Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

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

Kaneko, T.; CREST/JST, Tokyo 102-0075; Baba, K.

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changingmore » a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.« less

Theoretical derivation of anodizing current and comparison between fitted curves and measured curves under different conditions.

PubMed

Chong, Bin; Yu, Dongliang; Jin, Rong; Wang, Yang; Li, Dongdong; Song, Ye; Gao, Mingqi; Zhu, Xufei

2015-04-10

Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current j(ion) = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.

Theoretical derivation of anodizing current and comparison between fitted curves and measured curves under different conditions

NASA Astrophysics Data System (ADS)

Chong, Bin; Yu, Dongliang; Jin, Rong; Wang, Yang; Li, Dongdong; Song, Ye; Gao, Mingqi; Zhu, Xufei

2015-04-01

Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current jion = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.

Ionic Liquids as Unforeseen Assets to Fight Life-Threatening Mycotic Diseases.

PubMed

Hartmann, Diego O; Petkovic, Marija; Silva Pereira, Cristina

2016-01-01

Ionic liquids discovery has celebrated 100 years. They consist solely of ions, one of which is typically organic and asymmetrical. Remarkable physical and chemical properties stirred their use as alternative solvents in many chemical processes. The recent demonstration of their occurrence in nature might boost their interest in biological sciences. In the search of mechanistic understandings of ionic liquids' ecotoxicological impacts in fungi, we have analyzed the proteome, transcriptome, and metabolome responses to this chemical stress. Data illuminated new hypotheses that altered our research path - exploit ionic liquids as tools for the discovery of pathways and metabolites that may impact fungal development and pathogenicity. As we get closer to solve the primary effects of each ionic liquid family and their specific gene targets, the vision of developing antifungal ionic liquids and/or materials, by taking advantage of elegant progresses in this field, might become a reality. Task-designed formulations may improve the performance of conventional antifungal drugs, build functional coatings for reducing allergens production, or aid in the recovery of antifungal plant polymers. The frontier research in this cross-disciplinary field may provide us unforeseen means to address the global concern of mycotic diseases. Pathogenic and opportunistic fungi are responsible for numerous infections, killing annually nearly 1.5 million immunocompromised individuals worldwide, a similar rate to malaria or tuberculosis. This perspective will review our major findings and current hypotheses, contextualizing how they might bring us closer to efficient strategies to prevent and fight mycotic diseases.

A four-diode full-wave ionic current rectifier based on bipolar membranes: overcoming the limit of electrode capacity.

PubMed

Gabrielsson, Erik O; Janson, Per; Tybrandt, Klas; Simon, Daniel T; Berggren, Magnus

2014-08-13

Full-wave rectification of ionic currents is obtained by constructing the typical four-diode bridge out of ion conducting bipolar membranes. Together with conjugated polymer electrodes addressed with alternating current, the bridge allows for generation of a controlled ionic direct current for extended periods of time without the production of toxic species or gas typically arising from electrode side-reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extremely Low Operating Current Resistive Memory Based on Exfoliated 2D Perovskite Single Crystals for Neuromorphic Computing.

PubMed

Tian, He; Zhao, Lianfeng; Wang, Xuefeng; Yeh, Yao-Wen; Yao, Nan; Rand, Barry P; Ren, Tian-Ling

2017-12-26

Extremely low energy consumption neuromorphic computing is required to achieve massively parallel information processing on par with the human brain. To achieve this goal, resistive memories based on materials with ionic transport and extremely low operating current are required. Extremely low operating current allows for low power operation by minimizing the program, erase, and read currents. However, materials currently used in resistive memories, such as defective HfO x , AlO x , TaO x , etc., cannot suppress electronic transport (i.e., leakage current) while allowing good ionic transport. Here, we show that 2D Ruddlesden-Popper phase hybrid lead bromide perovskite single crystals are promising materials for low operating current nanodevice applications because of their mixed electronic and ionic transport and ease of fabrication. Ionic transport in the exfoliated 2D perovskite layer is evident via the migration of bromide ions. Filaments with a diameter of approximately 20 nm are visualized, and resistive memories with extremely low program current down to 10 pA are achieved, a value at least 1 order of magnitude lower than conventional materials. The ionic migration and diffusion as an artificial synapse is realized in the 2D layered perovskites at the pA level, which can enable extremely low energy neuromorphic computing.

Dual patch voltage clamp study of low membrane resistance astrocytes in situ.

PubMed

Ma, Baofeng; Xu, Guangjin; Wang, Wei; Enyeart, John J; Zhou, Min

2014-03-17

Whole-cell patch clamp recording has been successfully used in identifying the voltage-dependent gating and conductance properties of ion channels in a variety of cells. However, this powerful technique is of limited value in studying low membrane resistance cells, such as astrocytes in situ, because of the inability to control or accurately measure the real amplitude of command voltages. To facilitate the study of ionic conductances of astrocytes, we have developed a dual patch recording method which permits membrane current and membrane potential to be simultaneously recorded from astrocytes in spite of their extraordinarily low membrane resistance. The utility of this technique is demonstrated by measuring the voltage-dependent activation of the inwardly rectifying K+ current abundantly expressed in astrocytes and multiple ionic events associated with astrocytic GABAA receptor activation. This protocol can be performed routinely in the study of astrocytes. This method will be valuable for identifying and characterizing the individual ion channels that orchestrate the electrical activity of low membrane resistance cells.

Current rectification for transport of room-temperature ionic liquids through conical nanopores

DOE PAGES

Jiang, Xikai; Liu, Ying; Qiao, Rui

2016-02-09

Here, we studied the transport of room-temperature ionic liquids (RTILs) through charged conical nanopores using a Landau-Ginzburg-type continuum model that takes steric effect and strong ion-ion correlations into account. When the surface charge is uniform on the pore wall, weak current rectification is observed. When the charge density near the pore base is removed, the ionic current is greatly suppressed under negative bias voltage while nearly unchanged under positive bias voltage, thereby leading to enhanced current rectification. These predictions agree qualitatively with prior experimental observations, and we elucidated them by analyzing the different components of the ionic current and themore » structural changes of electrical double layers (EDLs) at the pore tip under different bias voltages and surface charge patterns. These analyses reveal that the different modifications of the EDL structure near the pore tip by the positive and negative bias voltages cause the current rectification and the observed dependence on the distribution of surface charge on the pore wall. The fact that the current rectification phenomena are captured qualitatively by the simple model originally developed for describing EDLs at equilibrium conditions suggests that this model may be promising for understanding the ionic transport under nonequilibrium conditions when the EDL structure is strongly perturbed by external fields.« less

[Atomic/ionic fluorescence in microwave plasma torch discharge with excitation of high current and microsecond pulsed hollow cathode lamp: Ca atomic/ionic fluorescence spectrometry].

PubMed

Gong, Zhen-bin; Liang, Feng; Yang, Peng-yuan; Jin, Qin-han; Huang, Ben-li

2002-02-01

A system of atomic and ionic fluorescence spectrometry in microwave plasma torch (MPT) discharge excited by high current microsecond pulsed hollow cathode lamp (HCMP HCL) has been developed. The operation conditions for Ca atomic and ionic fluorescence spectrometry have been optimized. Compared with atomic fluorescence spectrometry (AFS) in argon microwave induced plasma (MIP) and MPT with the excitation of direct current and conventional pulsed HCL, the system with HCMP HCL excitation can improve AFS and ionic fluorescence spectrometry (IFS) detection limits in MPT atomizer and ionizer. Detection limits (3 sigma) with HCMP HCL-MPT-AFS/IFS are 10.1 ng.mL-1 for Ca I 422.7 nm, 14.6 ng.mL-1 for Ca II 393.4 nm, and 37.4 ng.mL-1 for Ca II 396.8 nm, respectively.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Student Conceptions of Ionic Compounds in Solution and the Influences of Sociochemical Norms on Individual Learning

ERIC Educational Resources Information Center

Warfa, Abdi-Rizak M.

2013-01-01

Using the symbolic interactionist perspective that meaning is constituted as individuals interact with one another, this study examined how group thinking during cooperative inquiry-based activity on chemical bonding theories shaped and influenced college students' understanding of the properties of ionic compounds in solution. The analysis…

Cellulose ionics: switching ionic diode responses by surface charge in reconstituted cellulose films.

PubMed

Aaronson, Barak D B; Wigmore, David; Johns, Marcus A; Scott, Janet L; Polikarpov, Igor; Marken, Frank

2017-09-25

Cellulose films as well as chitosan-modified cellulose films of approximately 5 μm thickness, reconstituted from ionic liquid media onto a poly(ethylene-terephthalate) (PET, 6 μm thickness) film with a 5, 10, 20, or 40 μm diameter laser-drilled microhole, show significant current rectification in aqueous NaCl. Reconstituted α-cellulose films provide "cationic diodes" (due to predominant cation conductivity) whereas chitosan-doped cellulose shows "anionic diode" effects (due to predominant anion conductivity). The current rectification, or "ionic diode" behaviour, is investigated as a function of NaCl concentration, pH, microhole diameter, and molecular weight of the chitosan dopant. Future applications are envisaged exploiting the surface charge induced switching of diode currents for signal amplification in sensing.

Non-haloaluminate room-temperature ionic liquids in electrochemistry--a review.

PubMed

Buzzeo, Marisa C; Evans, Russell G; Compton, Richard G

2004-08-20

Some twenty-five years after they first came to prominence as alternative electrochemical solvents, room temperature ionic liquids (RTILs) are currently being employed across an increasingly wide range of chemical fields. This review examines the current state of ionic liquid-based electrochemistry, with particular focus on the work of the last decade. Being composed entirely of ions and possesing wide electrochemical windows (often in excess of 5 volts), it is not difficult to see why these compounds are seen by electrochemists as attractive potential solvents. Accordingly, an examination of the pertinent properties of ionic liquids is presented, followed by an assessment of their application to date across the various electrochemical disciplines, concluding with an outlook viewing current problems and directions.

Single-molecule nanopore enzymology

PubMed Central

Wloka, Carsten; Maglia, Giovanni

2017-01-01

Biological nanopores are a class of membrane proteins that open nanoscale water-conduits in biological membranes. When they are reconstituted in artificial membranes and a bias voltage is applied across the membrane, the ionic current passing through individual nanopores can be used to monitor chemical reactions, to recognize individual molecules and, of most interest, to sequence DNA. More recently, proteins and enzymes have started being analysed with nanopores. Monitoring enzymatic reactions with nanopores, i.e. nanopore enzymology, has the unique advantage that it allows long-timescale observations of native proteins at the single-molecule level. Here we describe the approaches and challenges in nanopore enzymology. PMID:28630164

Effect of surface bilayer charges on the magnetic field around ionic channels

NASA Astrophysics Data System (ADS)

Gomes Soares, Marília Amável; Cortez, Celia Martins; Oliveira Cruz, Frederico Alan de; Silva, Dilson

2017-01-01

In this work, we present a physic-mathematical model for representing the ion transport through membrane channels, in special Na+ and K+-channels, and discuss the influence of surface bilayer charges on the magnetic field behavior around the ionic current. The model was composed of a set of equations, including: a nonlinear differential Poisson-Boltzmann equation which usually allows to estimate the surface potentials and electric potential profile across membrane; equations for the ionic flux through channel and the ionic current density based on Armstrong's model for Na+ and K+ permeability and other Physics concepts; and a magnetic field expression derived from the classical Ampère equation. Results from computational simulations using the finite element method suggest that the ionic permeability is strongly dependent of surface bilayer charges, the current density through a K+-channel is very less sensible to temperature changes than the current density through a Na+- channel, active Na+-channels do not directly interfere with the K+-channels around, and vice-versa, since the magnetic perturbation generated by an active channel is of short-range.

Competition between ionic adsorption and desorption on electrochemical double layer capacitor electrodes in acetonitrile solutions at different currents and temperatures

NASA Astrophysics Data System (ADS)

Park, Sieun; Kang, Seok-Won; Kim, Ketack

2017-12-01

The operation of electrochemical double layer capacitors at high currents and viscosities and at low temperatures is difficult. Under these conditions, ion transport is limited, and some of the electrode area is unavailable for adsorption, which results in a low capacitance. Increasing the temperature helps to increase the ionic movement, leading to enhanced adsorption and increased capacitance. In contrast, ion desorption (self-discharge) surpasses the capacitance improvement when ions gain a high amount of energy with increasing temperature. For example, temperatures as high as 70 °C cause a very high rate of ionic desorption in acetonitrile solutions in which the individual properties of the two electrolytes-tetraethylammonium tetrafluoroborate (TEA BF4) and ethylmethylimidazolium tetrafluoroborate (EMI BF4)-are not distinguishable. The capacitance improvement and self-discharge are balanced, resulting in a capacitance peak at mid-range temperatures, i.e., 35-45 °C, in the more viscous electrolyte, i.e., TEA BF4. The less viscous electrolyte, i.e., EMI BF4 has a wider capacitance peak from 25 to 45 °C and higher capacitance than that of TEA BF4. Because the maximum power is obtained in the mid-temperature range (35-45 °C), it is necessary to control the viscosity and temperature to obtain the maximum power in a given device.

Thermodynamics, electrostatics, and ionic current in nanochannels grafted with pH-responsive end-charged polyelectrolyte brushes.

PubMed

Chen, Guang; Das, Siddhartha

2017-03-01

In this paper, we study the thermodynamics, electrostatics, and an external electric field driven ionic current in a pH-responsive, end-charged polyelectrolyte (PE) brush grafted nanochannel. By employing a mean field theory, we unravel a highly nonintuitive interplay of pH and electrolyte salt concentration in dictating the height of the end-charged PE brush. Larger pH or weak hydrogen ion concentration leads to maximum ionization of the charge-producing group-as a consequence, the resulting the electric double layer (EDL) energy get maximized causing a maximum deviation of the brush height from the value (d 0 ) of the uncharged brush. This deviation may result in enhancement or lowering of the brush height as compared to d 0 depending on whether the PE end locates lower or higher than h/2 (h is the nanochannel half height) and the salt concentration. Subsequently, we use this combined PE-brush-configuration-EDL-electrostatics framework to compute the ionic current in the nanochannel. We witness that the ionic current for smaller pH is much larger despite the corresponding magnitude of the EDL electrostatic potential being much smaller-this stems from the presence of a much larger concentration of H+ ions at small pH and the fact that H+ ions have very large mobilities. In fact, this ionic current shows a steep variation with pH that can be useful in exploring new designs for applications involving quantification and characterization of ionic current in PE-brush-grafted nanochannels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

J Wave Syndromes: History and Current Controversies

PubMed Central

Liu, Tong; Zheng, Jifeng

2016-01-01

The concept of J wave syndromes was first proposed in 2004 by Yan et al for a spectrum of electrocardiographic (ECG) manifestations of prominent J waves that are associated with a potential to predispose affected individuals to ventricular fibrillation (VF). Although the concept of J wave syndromes is widely used and accepted, there has been tremendous debate over the definition of J wave, its ionic and cellular basis and arrhythmogenic mechanism. In this review article, we attempted to discuss the history from which the concept of J wave syndromes (JWS) is evolved and current controversies in JWS. PMID:27721848

Ionic size effects to molecular solvation energy and to ion current across a channel resulted from the nonuniform size-modified PNP equations.

PubMed

Qiao, Yu; Tu, Bin; Lu, Benzhuo

2014-05-07

Ionic finite size can impose considerable effects to both the equilibrium and non-equilibrium properties of a solvated molecular system, such as the solvation energy, ionic concentration, and transport in a channel. As discussed in our former work [B. Lu and Y. C. Zhou, Biophys. J. 100, 2475 (2011)], a class of size-modified Poisson-Boltzmann (PB)/Poisson-Nernst-Planck (PNP) models can be uniformly studied through the general nonuniform size-modified PNP (SMPNP) equations deduced from the extended free energy functional of Borukhov et al. [I. Borukhov, D. Andelman, and H. Orland, Phys. Rev. Lett. 79, 435 (1997)] This work focuses on the nonuniform size effects to molecular solvation energy and to ion current across a channel for real biomolecular systems. The main contributions are: (1) we prove that for solvation energy calculation with nonuniform size effects (through equilibrium SMPNP simulation), there exists a simplified approximation formulation which is the same as the widely used one in PB community. This approximate form avoids integration over the whole domain and makes energy calculations convenient. (2) Numerical calculations show that ionic size effects tend to negate the solvation effects, which indicates that a higher molecular solvation energy (lower absolute value) is to be predicted when ionic size effects are considered. For both calculations on a protein and a DNA fragment systems in a 0.5M 1:1 ionic solution, a difference about 10 kcal/mol in solvation energies is found between the PB and the SMPNP predictions. Moreover, it is observed that the solvation energy decreases as ionic strength increases, which behavior is similar as those predicted by the traditional PB equation (without size effect) and by the uniform size-modified Poisson-Boltzmann equation. (3) Nonequilibrium SMPNP simulations of ion permeation through a gramicidin A channel show that the ionic size effects lead to reduced ion current inside the channel compared with the results without considering size effects. As a component of the current, the drift term is the main contribution to the total current. The ionic size effects to the total current almost come through the drift term, and have little influence on the diffusion terms in SMPNP.

Modulation of Molecular Flux Using a Graphene Nanopore Capacitor.

PubMed

Shankla, Manish; Aksimentiev, Aleksei

2017-04-20

Modulation of ionic current flowing through nanoscale pores is one of the fundamental biological processes. Inspired by nature, nanopores in synthetic solid-state membranes are being developed to enable rapid analysis of biological macromolecules and to serve as elements of nanofludic circuits. Here, we theoretically investigate ion and water transport through a graphene-insulator-graphene membrane containing a single, electrolyte-filled nanopore. By means of all-atom molecular dynamics simulations, we show that the charge state of such a graphene nanopore capacitor can regulate both the selectivity and the magnitude of the nanopore ionic current. At a fixed transmembrane bias, the ionic current can be switched from being carried by an equal mixture of cations and anions to being carried almost exclusively by either cationic or anionic species, depending on the sign of the charge assigned to both plates of the capacitor. Assigning the plates of the capacitor opposite sign charges can either increase the nanopore current or reduce it substantially, depending on the polarity of the bias driving the transmembrane current. Facilitated by the changes of the nanopore surface charge, such ionic current modulations are found to occur despite the physical dimensions of the nanopore being an order of magnitude larger than the screening length of the electrolyte. The ionic current rectification is accompanied by a pronounced electro-osmotic effect that can transport neutral molecules such as proteins and drugs across the solid-state membrane and thereby serve as an interface between electronic and chemical signals.

Cell cycle-related fluctuations in transcellular ionic currents and plasma membrane Ca2+/Mg2+ ATPase activity during early cleavages of Lymnaea stagnalis embryos.

PubMed

Zivkovic, Danica; Créton, Robbert; Dohmen, René

1991-08-01

During the first four mitotic division cycles of Lymnaea stagnalis embryos, we have detected cell cycle-dependent changes in the pattern of transcellular ionic currents and membrane-bound Ca 2+ -stimulated ATPase activity. Ionic currents ranging from 0.05 to 2.50 μA/cm 2 have been measured using the vibrating probe technique. Enzyme activity was detected using Ando's cytochemical method (Ando et al. 1981) which reveals Ca 2+ /Mg 2+ ATPase localization at the ultrastructural level, and under high-stringency conditions with respect to calcium availability, it reveals Ca 2+ -stimulated ATPase. The ionic currents and Ca 2+ -stimulated ATPase localization have in common that important changes occur during the M-phase of the cell cycles. Minimal outward current at the vegetal pole coincides with metaphase/anaphase. Maximal inward current at the animal pole coincides with the onset of cytokinesis at that pole. Ca 2+ -stimulated ATPase is absent from one half of the embryo at metaphase/anaphase of the two- and four-cell stage, whereas it is present in all cells during the remaining part of the cell cycle. Since fluctuations of cytosolic free calcium concentrations appear to correlate with both karyokinesis and cytokinesis, we speculate that part of the cyclic pattern of Ca 2+ -stimulated ATPase localization and of the transcellular ionic currents reflects the elevation of cytosolic free calcium concentration during the M-phase.

Electrochemical energy storage device based on carbon dioxide as electroactive species

DOEpatents

Nemeth, Karoly; van Veenendaal, Michel Antonius; Srajer, George

2013-03-05

An electrochemical energy storage device comprising a primary positive electrode, a negative electrode, and one or more ionic conductors. The ionic conductors ionically connect the primary positive electrode with the negative electrode. The primary positive electrode comprises carbon dioxide (CO.sub.2) and a means for electrochemically reducing the CO.sub.2. This means for electrochemically reducing the CO.sub.2 comprises a conductive primary current collector, contacting the CO.sub.2, whereby the CO.sub.2 is reduced upon the primary current collector during discharge. The primary current collector comprises a material to which CO.sub.2 and the ionic conductors are essentially non-corrosive. The electrochemical energy storage device uses CO.sub.2 as an electroactive species in that the CO.sub.2 is electrochemically reduced during discharge to enable the release of electrical energy from the device.

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

PubMed

Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

2015-10-20

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

Ionic Liquids as Extraction Media for Metal Ions

NASA Astrophysics Data System (ADS)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

PubMed

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-12-04

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO₂) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO₂ sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

PubMed Central

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-01-01

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

Ionic liquids: Promising green solvents for lignocellulosic biomass utilization

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

Yoo, Chang Geun; Pu, Yunqiao; Ragauskas, Arthur J.

Ionic liquids are effective solvents/media for the utilization of lignocellulosic biomass. The unique properties of ionic liquids enable them to effectively dissolve and/or convert the biomass into various types of products. This review aims to cover the latest progress achieved in applications of ionic liquids on biomass conversion and analysis. Specifically, several recently developed approaches on how to overcome current challenges on the use of ionic liquids in the biomass conversion were highlighted. Here, recent studies addressing the potential applications of ionic liquids for the production of novel biomass-derived chemicals and materials were also discussed.

Ionic liquids: Promising green solvents for lignocellulosic biomass utilization

DOE PAGES

Yoo, Chang Geun; Pu, Yunqiao; Ragauskas, Arthur J.

2017-06-01

Ionic liquids are effective solvents/media for the utilization of lignocellulosic biomass. The unique properties of ionic liquids enable them to effectively dissolve and/or convert the biomass into various types of products. This review aims to cover the latest progress achieved in applications of ionic liquids on biomass conversion and analysis. Specifically, several recently developed approaches on how to overcome current challenges on the use of ionic liquids in the biomass conversion were highlighted. Here, recent studies addressing the potential applications of ionic liquids for the production of novel biomass-derived chemicals and materials were also discussed.

A new theoretical model for transmembrane potential and ion currents induced in a spherical cell under low frequency electromagnetic field.

PubMed

Zheng, Yu; Gao, Yang; Chen, Ruijuan; Wang, Huiquan; Dong, Lei; Dou, Junrong

2016-10-01

Time-varying electromagnetic fields (EMF) can induce some physiological effects in neuronal tissues, which have been explored in many applications such as transcranial magnetic stimulation. Although transmembrane potentials and induced currents have already been the subjects of many theoretical studies, most previous works about this topic are mainly completed by utilizing Maxwell's equations, often by solving a Laplace equation. In previous studies, cells were often considered to be three-compartment models with different electroconductivities in different regions (three compartments are often intracellular regions, membrane, and extracellular regions). However, models like that did not take dynamic ion channels into consideration. Therefore, one cannot obtain concrete ionic current changes such as potassium current change or sodium current change by these models. The aim of the present work is to present a new and more detailed model for calculating transmembrane potentials and ionic currents induced by time-varying EMF. Equations used in the present paper originate from Nernst-Plank equations, which are ionic current-related equations. The main work is to calculate ionic current changes induced by EMF exposure, and then transmembrane potential changes are calculated with Hodgkin-Huxley model. Bioelectromagnetics. 37:481-492, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Sodium influxes in internally perfused squid giant axon during voltage clamp.

PubMed

Atwater, I; Bezanilla, F; Rojas, E

1969-05-01

1. An experimental method for measuring ionic influxes during voltage clamp in the giant axon of Dosidicus is described; the technique combines intracellular perfusion with a method for controlling membrane potential.2. Sodium influx determinations were carried out while applying rectangular pulses of membrane depolarization. The ratio ;measured sodium influx/computed ionic flux during the early current' is 0.92 +/- 0.12.3. Plots of measured sodium influx and computed ionic flux during the early current against membrane potential are very similar. There was evidence that the membrane potential at which the sodium influx vanishes is the potential at which the early current reverses.

Ionic mechanisms and Ca2+ dynamics underlying the glucose response of pancreatic β cells: a simulation study

PubMed Central

Cha, Chae Young; Nakamura, Yasuhiko; Himeno, Yukiko; Wang, JianWu; Fujimoto, Shinpei; Inagaki, Nobuya; Earm, Yung E

2011-01-01

To clarify the mechanisms underlying the pancreatic β-cell response to varying glucose concentrations ([G]), electrophysiological findings were integrated into a mathematical cell model. The Ca2+ dynamics of the endoplasmic reticulum (ER) were also improved. The model was validated by demonstrating quiescent potential, burst–interburst electrical events accompanied by Ca2+ transients, and continuous firing of action potentials over [G] ranges of 0–6, 7–18, and >19 mM, respectively. These responses to glucose were completely reversible. The action potential, input impedance, and Ca2+ transients were in good agreement with experimental measurements. The ionic mechanisms underlying the burst–interburst rhythm were investigated by lead potential analysis, which quantified the contributions of individual current components. This analysis demonstrated that slow potential changes during the interburst period were attributable to modifications of ion channels or transporters by intracellular ions and/or metabolites to different degrees depending on [G]. The predominant role of adenosine triphosphate–sensitive K+ current in switching on and off the repetitive firing of action potentials at 8 mM [G] was taken over at a higher [G] by Ca2+- or Na+-dependent currents, which were generated by the plasma membrane Ca2+ pump, Na+/K+ pump, Na+/Ca2+ exchanger, and TRPM channel. Accumulation and release of Ca2+ by the ER also had a strong influence on the slow electrical rhythm. We conclude that the present mathematical model is useful for quantifying the role of individual functional components in the whole cell responses based on experimental findings. PMID:21708953

Hydrodynamic model of temperature change in open ionic channels.

PubMed Central

Chen, D P; Eisenberg, R S; Jerome, J W; Shu, C W

1995-01-01

Most theories of open ionic channels ignore heat generated by current flow, but that heat is known to be significant when analogous currents flow in semiconductors, so a generalization of the Poisson-Nernst-Planck theory of channels, called the hydrodynamic model, is needed. The hydrodynamic theory is a combination of the Poisson and Euler field equations of electrostatics and fluid dynamics, conservation laws that describe diffusive and convective flow of mass, heat, and charge (i.e., current), and their coupling. That is to say, it is a kinetic theory of solute and solvent flow, allowing heat and current flow as well, taking into account density changes, temperature changes, and electrical potential gradients. We integrate the equations with an essentially nonoscillatory shock-capturing numerical scheme previously shown to be stable and accurate. Our calculations show that 1) a significant amount of electrical energy is exchanged with the permeating ions; 2) the local temperature of the ions rises some tens of degrees, and this temperature rise significantly alters for ionic flux in a channel 25 A long, such as gramicidin-A; and 3) a critical parameter, called the saturation velocity, determines whether ionic motion is overdamped (Poisson-Nernst-Planck theory), is an intermediate regime (called the adiabatic approximation in semiconductor theory), or is altogether unrestricted (requiring the full hydrodynamic model). It seems that significant temperature changes are likely to accompany current flow in the open ionic channel. PMID:8599638

Pharmacological characterization of ionic currents that regulate high-frequency spontaneous activity of electromotor neurons in the weakly electric fish, Apteronotus leptorhynchus.

PubMed

Smith, G Troy

2006-01-01

The neural circuit that controls the electric organ discharge (EOD) of the brown ghost knifefish (Apteronotus leptorhynchus) contains two spontaneous oscillators. Both pacemaker neurons in the medulla and electromotor neurons (EMNs) in the spinal cord fire spontaneously at frequencies of 500-1,000 Hz to control the EOD. These neurons continue to fire in vitro at frequencies that are highly correlated with in vivo EOD frequency. Previous studies used channel blocking drugs to pharmacologically characterize ionic currents that control high-frequency firing in pacemaker neurons. The goal of the present study was to use similar techniques to investigate ionic currents in EMNs, the other type of spontaneously active neuron in the electromotor circuit. As in pacemaker neurons, high-frequency firing of EMNs was regulated primarily by tetrodotoxin-sensitive sodium currents and by potassium currents that were sensitive to 4-aminopyridine and kappaA-conotoxin SIVA, but resistant to tetraethylammonium. EMNs, however, differed from pacemaker neurons in their sensitivity to some channel blocking drugs. Alpha-dendrotoxin, which blocks a subset of Kv1 potassium channels, increased firing rates in EMNs, but not pacemaker neurons; and the sodium channel blocker muO-conotoxin MrVIA, which reduced firing rates of pacemaker neurons, had no effect on EMNs. These results suggest that similar, but not identical, ionic currents regulate high-frequency firing in EMNs and pacemaker neurons. The differences in the ionic currents expressed in pacemaker neurons and EMNs might be related to differences in the morphology, connectivity, or function of these two cell types.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1996-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1997-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

ERRORS IN APPLYING LOW IONIC-STRENGTH ACTIVITY COEFFICIENT ALGORITHMS TO HIGHER IONIC-STRENGTH AQUATIC MEDIA

EPA Science Inventory

The toxicological and regulatory communities are currently exploring the use of the free-ion-activity (FIA) model both alone and in conjunction with the biotic ligand model (BLM) as a means of reducing uncertainties in current methods for assessing metals bioavailability from aqu...

Proteins in Ionic Liquids: Current Status of Experiments and Simulations.

PubMed

Schröder, Christian

2017-04-01

In the last two decades, while searching for interesting applications of ionic liquids as potent solvents, their solvation properties and their general impact on biomolecules, and in particular on proteins, gained interest. It turned out that ionic liquids are excellent solvents for protein refolding and crystallization. Biomolecules showed increased solubilities and stabilities, both operational and thermal, in ionic liquids, which also seem to prevent self-aggregation during solubilization. Biomolecules can be immobilized, e.g. in highly viscous ionic liquids, for particular biochemical processes and can be designed to some extent by the proper choice of the ionic liquid cations and anions, which can be characterized by the Hofmeister series.

A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

PubMed

Ghosh, Arnab; Manjunatha, Revanasiddappa; Kumar, Rajat; Mitra, Sagar

2016-12-14

Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li 2 S 2 and Li 2 S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn 3 O 4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g -1 is achieved against lithium after 200 cycles at a current rate of 2 A g -1 with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g -1 , the composite electrode exhibited an initial capacity of 1015 mA h g -1 and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn 3 O 4 . This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

Simulation of polymer translocation through protein channels

PubMed Central

Muthukumar, M.; Kong, C. Y.

2006-01-01

A modeling algorithm is presented to compute simultaneously polymer conformations and ionic current, as single polymer molecules undergo translocation through protein channels. The method is based on a combination of Langevin dynamics for coarse-grained models of polymers and the Poisson–Nernst–Planck formalism for ionic current. For the illustrative example of ssDNA passing through the α-hemolysin pore, vivid details of conformational fluctuations of the polymer inside the vestibule and β-barrel compartments of the protein pore, and their consequent effects on the translocation time and extent of blocked ionic current are presented. In addition to yielding insights into several experimentally reported puzzles, our simulations offer experimental strategies to sequence polymers more efficiently. PMID:16567657

Sodium influxes in internally perfused squid giant axon during voltage clamp

PubMed Central

Atwater, I.; Bezanilla, F.; Rojas, E.

1969-01-01

1. An experimental method for measuring ionic influxes during voltage clamp in the giant axon of Dosidicus is described; the technique combines intracellular perfusion with a method for controlling membrane potential. 2. Sodium influx determinations were carried out while applying rectangular pulses of membrane depolarization. The ratio `measured sodium influx/computed ionic flux during the early current' is 0·92 ± 0·12. 3. Plots of measured sodium influx and computed ionic flux during the early current against membrane potential are very similar. There was evidence that the membrane potential at which the sodium influx vanishes is the potential at which the early current reverses. PMID:5767887

Ionic calcium determination in skim milk with molecular probes and front-face fluorescence spectroscopy: simple linear regression.

PubMed

Gangidi, R R; Metzger, L E

2006-11-01

The purpose of this study was to determine if the ionic calcium content of skim milk could be determined using molecular probes and front-face fluorescence spectroscopy. Current methods for determining ionic calcium are not sensitive, overestimate ionic calcium, or require complex procedures. Molecular probes designed specifically for measuring ionic calcium could potentially be used to determine the ionic calcium content of skim milk. The goal of the current study was to develop foundation methods for future studies to determine ionic calcium directly in skim milk and other dairy products with molecular probes and fluorescence spectroscopy. In this study, the effect of pH on calcium-sensitive fluorescent probe (Rhod-5N and Fluo-5N) performance using various concentrations of skim milk was determined. The pH of diluted skim milk (1.9 to 8.9% skim milk), was adjusted to either 6.2 or 7.0, after which the samples were analyzed with fluorescent probes (1 microM) and front-face fluorescence spectroscopy. The ionic calcium content of each sample was also determined using a calcium ion-selective electrode. The results demonstrated that the ionic calcium content of each sample was highly correlated (R2 > 0.989) with the fluorescence intensities of the probe-calcium adduct using simple linear regression. Higher than suggested ionic calcium contents of 1,207 and 1,973 microM were determined with the probes (Fluo-5N and Rhod-5N) in diluted skim milk with pH 7.0 and 6.2, respectively. The fluorescence intensity of the probe-calcium adduct decreased with a decrease in pH for the same ionic calcium concentration. This study demonstrates that Fluo-5N and Rhod-5N can be used to determine the ionic-calcium content of diluted milk with front-face fluorescence spectroscopy. Furthermore, these probes may also have the potential to determine the ionic calcium content of undiluted skim milk.

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

Davidson, Jacob D.; Goulbourne, N. C.

2011-01-01

Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an optimal electromechanical conversion efficiency for bending actuation is achieved by using an ionic liquid where only a relatively small fraction of the ionic liquid ions exist as free ions. Conversely, if it is desired to increase the overall amount of charge transferred, an ionic liquid with a large fraction of free ions should be used. These theoretical considerations are found to be in good qualitative agreement with recent experimental results.

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

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

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

Electrodiffusion kinetics of ionic transport in a simple membrane channel.

PubMed

Valent, Ivan; Petrovič, Pavol; Neogrády, Pavel; Schreiber, Igor; Marek, Miloš

2013-11-21

We employ numerical techniques for solving time-dependent full Poisson-Nernst-Planck (PNP) equations in 2D to analyze transient behavior of a simple ion channel subject to a sudden electric potential jump across the membrane (voltage clamp). Calculated spatiotemporal profiles of the ionic concentrations and electric potential show that two principal exponential processes can be distinguished in the electrodiffusion kinetics, in agreement with original Planck's predictions. The initial fast process corresponds to the dielectric relaxation, while the steady state is approached in a second slower exponential process attributed to the nonlinear ionic redistribution. Effects of the model parameters such as the channel length, height of the potential step, boundary concentrations, permittivity of the channel interior, and ionic mobilities on electrodiffusion kinetics are studied. Numerical solutions are used to determine spatiotemporal profiles of the electric field, ionic fluxes, and both the conductive and displacement currents. We demonstrate that the displacement current is a significant transient component of the total electric current through the channel. The presented results provide additional information about the classical voltage-clamp problem and offer further physical insights into the mechanism of electrodiffusion. The used numerical approach can be readily extended to multi-ionic models with a more structured domain geometry in 2D or 3D, and it is directly applicable to other systems, such as synthetic nanopores, nanofluidic channels, and nanopipettes.

Simultaneous recording of electrical activity and the underlying ionic currents in NG108-15 cells cultured on gold substrate.

PubMed

Acosta-García, Ma Cristina; Morales-Reyes, Israel; Jiménez-Anguiano, Anabel; Batina, Nikola; Castellanos, N P; Godínez-Fernández, R

2018-02-01

This paper shows the simultaneous recording of electrical activity and the underlying ionic currents by using a gold substrate to culture NG108-15 cells. Cells grown on two different substrates (plastic Petri dishes and gold substrates) were characterized quantitatively through scanning electron microscopy (SEM) as well as qualitatively by optical and atomic force microscopy (AFM). No significant differences were observed between the surface area of cells cultured on gold substrates and Petri dishes, as indicated by measurements performed on SEM images. We also evaluated the electrophysiological compatibility of the cells through standard patch-clamp experiments by analyzing features such as the resting potential, membrane resistance, ionic currents, etc. Cells grown on both substrates showed no significant differences in their dependency on voltage, as well as in the magnitude of the Na+ and K+ current density; however, cells cultured on the gold substrate showed a lower membrane capacitance when compared to those grown on Petri dishes. By using two separate patch-clamp amplifiers, we were able to record the membrane current with the conventional patch-clamp technique and through the gold substrate simultaneously. Furthermore, the proposed technique allowed us to obtain simultaneous recordings of the electrical activity (such as action potentials firing) and the underlying membrane ionic currents. The excellent conductivity of gold makes it possible to overcome important difficulties found in conventional electrophysiological experiments such as those presented by the resistance of the electrolytic bath solution. We conclude that the technique here presented constitutes a solution to the problem of the simultaneous recording of electrical activity and the underlying ionic currents, which for decades, had been solved only partially.

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A universal steady state I-V relationship for membrane current

NASA Technical Reports Server (NTRS)

Chernyak, Y. B.; Cohen, R. J. (Principal Investigator)

1995-01-01

A purely electrical mechanism for the gating of membrane ionic channel gives rise to a simple I-V relationship for membrane current. Our approach is based on the known presence of gating charge, which is an established property of the membrane channel gating. The gating charge is systematically treated as a polarization of the channel protein which varies with the external electric field and modifies the effective potential through which the ions migrate in the channel. Two polarization effects have been considered: 1) the up or down shift of the whole potential function, and 2) the change in the effective electric field inside the channel which is due to familiar effect of the effective reduction of the electric field inside a dielectric body because of the presence of surface charges on its surface. Both effects are linear in the channel polarization. The ionic current is described by a steady state solution of the Nernst-Planck equation with the potential directly controlled by the gating charge system. The solution describes reasonably well the steady state and peak-current I-V relationships for different channels, and when applied adiabatically, explains the time lag between the gating charge current and the rise of the ionic current. The approach developed can be useful as an effective way to model the ionic currents in axons, cardiac cells and other excitable tissues.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE PAGES

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; ...

2016-05-19

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

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

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Lithium-Air and ionic Liquids

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

Kellar, Michael

2015-09-01

The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less

Multichannel detection of ionic currents through two nanopores fabricated on integrated Si3N4 membranes.

PubMed

Yanagi, Itaru; Akahori, Rena; Aoki, Mayu; Harada, Kunio; Takeda, Ken-Ichi

2016-08-16

Integration of solid-state nanopores and multichannel detection of signals from each nanopore are effective measures for realizing high-throughput nanopore sensors. In the present study, we demonstrated fabrication of Si3N4 membrane arrays and the simultaneous measurement of ionic currents through two nanopores formed in two adjacent membranes. Membranes with thicknesses as low as 6.4 nm and small nanopores with diameters of less than 2 nm could be fabricated using the poly-Si sacrificial-layer process and multilevel pulse-voltage injection. Using the fabricated nanopore membranes, we successfully achieved simultaneous detection of clear ionic-current blockades when single-stranded short homopolymers (poly(dA)60) passed through two nanopores. In addition, we investigated the signal crosstalk and leakage current among separated chambers. When two nanopores were isolated on the front surface of the membrane, there was no signal crosstalk or leakage current between the chambers. However, when two nanopores were isolated on the backside of the Si substrate, signal crosstalk and leakage current were observed owing to high-capacitance coupling between the chambers and electrolysis of water on the surface of the Si substrate. The signal crosstalk and leakage current could be suppressed by oxidizing the exposed Si surface in the membrane chip. Finally, the observed ionic-current blockade when poly(dA)60 passed through the nanopore in the oxidized chip was approximately half of that observed in the non-oxidized chip.

Solid-State Ionic Diodes Demonstrated in Conical Nanopores

DOE PAGES

Plett, Timothy S.; Cai, Wenjia; Le Thai, Mya; ...

2017-02-27

Ionic transport at the nanoscale features phenomena that are not observed in larger systems. Nonlinear current–voltage curves characteristic of ionic diodes as well as ion selectivity are examples of effects observed at the nanoscale. Many man-made nanopore systems are inspired by biological channels in a cell membrane, thus measurements are often performed in aqueous solutions. Consequently, much less is known about ionic transport in nonaqueous systems, especially in solid-state electrolytes. Here we show ionic transport through single pores filled with gel electrolyte of poly(methyl methacrylate) (PMMA) doped with LiClO 4 in propylene carbonate. The system has no liquid interface andmore » the ionic transport occurs through the porous gel structure. We demonstrate that a conically shaped nanopore filled with the gel rectifies the current and works as a solid-state ionic diode.« less

DNA Sequence-Dependent Ionic Currents in Ultra-Small Solid-State Nanopores†

PubMed Central

Comer, Jeffrey

2016-01-01

Measurements of ionic currents through nanopores partially blocked by DNA have emerged as a powerful method for characterization of the DNA nucleotide sequence. Although the effect of the nucleotide sequence on the nanopore blockade current has been experimentally demonstrated, prediction and interpretation of such measurements remain a formidable challenge. Using atomic resolution computational approaches, here we show how the sequence, molecular conformation, and pore geometry affect the blockade ionic current in model solid-state nanopores. We demonstrate that the blockade current from a DNA molecule is determined by the chemical identities and conformations of at least three consecutive nucleotides. We find the blockade currents produced by the nucleotide triplets to vary considerably with their nucleotide sequence despite having nearly identical molecular conformations. Encouragingly, we find blockade current differences as large as 25% for single-base substitutions in ultra small (1.6 nm × 1.1 nm cross section; 2 nm length) solid-state nanopores. Despite the complex dependence of the blockade current on the sequence and conformation of the DNA triplets, we find that, under many conditions, the number of thymine bases is positively correlated with the current, whereas the number of purine bases and the presence of both purine and pyrimidines in the triplet are negatively correlated with the current. Based on these observations, we construct a simple theoretical model that relates the ion current to the base content of a solid-state nanopore. Furthermore, we show that compact conformations of DNA in narrow pores provide the greatest signal-to-noise ratio for single base detection, whereas reduction of the nanopore length increases the ionic current noise. Thus, the sequence dependence of nanopore blockade current can be theoretically rationalized, although the predictions will likely need to be customized for each nanopore type. PMID:27103233

Novel applications of ionic liquids in materials processing

NASA Astrophysics Data System (ADS)

Reddy, Ramana G.

2009-05-01

Ionic liquids are mixtures of organic and inorganic salts which are liquids at room temperature. Several potential applications of ionic liquids in the field of materials processing are electrowinning and electrodeposition of metals and alloys, electrolysis of active metals at low temperature, liquid-liquid extraction of metals. Results using 1-butyl-3-methylimidazolium chloride with AlCl3 at low temperatures yielded high purity aluminium deposits (>99.9% pure) and current efficiencies >98%. Titanium and aluminium were co-deposited with/without the addition of TiCl4 with up to 27 wt% Ti in the deposit with current efficiencies in the range of 78-85 %. Certain ionic liquids are potential replacements for thermal oils and molten salts as heat transfer fluids in solar energy applications due to high thermal stability, very low corrosivity and substantial sensible heat retentivity. The calculated storage densities for several chloride and fluoride ionic liquids are in the range of 160-210 MJ/m3. A 3-D mathematical model was developed to simulate the large scale electrowinning of aluminium. Since ionic liquids processing results in their low energy consumption, low pollutant emissions many more materials processing applications are expected in future.

Substantial Expansion of Detectable Size Range in Ionic Current Sensing through Pores by Using a Microfluidic Bridge Circuit.

PubMed

Yasaki, Hirotoshi; Yasui, Takao; Yanagida, Takeshi; Kaji, Noritada; Kanai, Masaki; Nagashima, Kazuki; Kawai, Tomoji; Baba, Yoshinobu

2017-10-11

Measuring ionic currents passing through nano- or micropores has shown great promise for the electrical discrimination of various biomolecules, cells, bacteria, and viruses. However, conventional measurements have shown there is an inherent limitation to the detectable particle volume (1% of the pore volume), which critically hinders applications to real mixtures of biomolecule samples with a wide size range of suspended particles. Here we propose a rational methodology that can detect samples with the detectable particle volume of 0.01% of the pore volume by measuring a transient current generated from the potential differences in a microfluidic bridge circuit. Our method substantially suppresses the background ionic current from the μA level to the pA level, which essentially lowers the detectable particle volume limit even for relatively large pore structures. Indeed, utilizing a microscale long pore structure (volume of 5.6 × 10 4 aL; height and width of 2.0 × 2.0 μm; length of 14 μm), we successfully detected various samples including polystyrene nanoparticles (volume: 4 aL), bacteria, cancer cells, and DNA molecules. Our method will expand the applicability of ionic current sensing systems for various mixed biomolecule samples with a wide size range, which have been difficult to measure by previously existing pore technologies.

Thermoelectricity in Heterogeneous Nanofluidic Channels.

PubMed

Li, Long; Wang, Qinggong

2018-05-01

Ionic fluids are essential to energy conversion, water desalination, drug delivery, and lab-on-a-chip devices. Ionic transport in nanoscale confinements and complex physical fields still remain elusive. Here, a nanofluidic system is developed using nanochannels of heterogeneous surface properties to investigate transport properties of ions under different temperatures. Steady ionic currents are observed under symmetric temperature gradients, which is equivalent to generating electricity using waste heat (e.g., electronic chips and solar panels). The currents increase linearly with temperature gradient and nonlinearly with channel size. Contributions to ion motion from temperatures and channel properties are evaluated for this phenomenon. The findings provide insights into the study of confined ionic fluids in multiphysical fields, and suggest applications in thermal energy conversion, temperature sensors, and chip-level thermal management. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of force generated by individual myosin heads in skinned rabbit psoas muscle fibers at low ionic strength.

PubMed

Sugi, Haruo; Abe, Takahiro; Kobayashi, Takakazu; Chaen, Shigeru; Ohnuki, Yoshiki; Saeki, Yasutake; Sugiura, Seiryo

2013-01-01

Although evidence has been presented that, at low ionic strength, myosin heads in relaxed skeletal muscle fibers form linkages with actin filaments, the effect of low ionic strength on contraction characteristics of Ca(2+)-activated muscle fibers has not yet been studied in detail. To give information about the mechanism of muscle contraction, we have examined the effect of low ionic strength on the mechanical properties and the contraction characteristics of skinned rabbit psoas muscle fibers in both relaxed and maximally Ca(2+)-activated states. By progressively decreasing KCl concentration from 125 mM to 0 mM (corresponding to a decrease in ionic strength μ from 170 mM to 50 mM), relaxed fibers showed changes in mechanical response to sinusoidal length changes and ramp stretches, which are consistent with the idea of actin-myosin linkage formation at low ionic strength. In maximally Ca(2+)-activated fibers, on the other hand, the maximum isometric force increased about twofold by reducing KCl concentration from 125 to 0 mM. Unexpectedly, determination of the force-velocity curves indicated that, the maximum unloaded shortening velocity Vmax, remained unchanged at low ionic strength. This finding indicates that the actin-myosin linkages, which has been detected in relaxed fibers at low ionic strength, are broken quickly on Ca(2+) activation, so that the linkages in relaxed fibers no longer provide any internal resistance against fiber shortening. The force-velocity curves, obtained at various levels of steady Ca(2+)-activated isometric force, were found to be identical if they are normalized with respect to the maximum isometric force. The MgATPase activity of muscle fibers during isometric force generation was found not to change appreciably at low ionic strength despite the two-fold increase in Ca(2+)-activated isometric force. These results can be explained in terms of enhancement of force generated by individual myosin heads, but not by any changes in kinetic properties of cyclic actin-myosin interaction.

Polarization of gold in nanopores leads to ion current rectification

DOE PAGES

Yang, Crystal; Hinkle, Preston; Menestrina, Justin; ...

2016-10-03

Biomimetic nanopores with rectifying properties are relevant components of ionic switches, ionic circuits, and biological sensors. Rectification indicates that currents for voltages of one polarity are higher than currents for voltages of the opposite polarity. Ion current rectification requires the presence of surface charges on the pore walls, achieved either by the attachment of charged groups or in multielectrode systems by applying voltage to integrated gate electrodes. Here we present a simpler concept for introducing surface charges via polarization of a thin layer of Au present at one entrance of a silicon nitride nanopore. In an electric field applied bymore » two electrodes placed in bulk solution on both sides of the membrane, the Au layer polarizes such that excess positive charge locally concentrates at one end and negative charge concentrates at the other end. Consequently, a junction is formed between zones with enhanced anion and cation concentrations in the solution adjacent to the Au layer. This bipolar double layer together with enhanced cation concentration in a negatively charged silicon nitride nanopore leads to voltage-controlled surface-charge patterns and ion current rectification. The experimental findings are supported by numerical modeling that confirm modulation of ionic concentrations by the Au layer and ion current rectification even in low-aspect ratio nanopores. Lastly, our findings enable a new strategy for creating ionic circuits with diodes and transistors.« less

Simulation of mechano-electrical transduction in the cochlea considering basilar membrane vibration and the ionic current of the inner hair cells

NASA Astrophysics Data System (ADS)

Lee, Sinyoung; Koike, Takuji

2018-05-01

The inner hair cells (IHCs) in the cochlea transduce mechanical vibration of the basilar membrane (BM), caused by sound pressure, to electrical signals that are transported along the acoustic nerve to the brain. The mechanical vibration of the BM and the ionic behaviors of the IHCs have been investigated. However, consideration of the ionic behavior of the IHCs related to mechanical vibration is necessary to investigate the mechano-electrical transduction of the cochlea. In this study, a finite-element model of the BM, which takes into account the non-linear activities of the outer hair cells (OHCs), and an ionic current model of IHC were combined. The amplitudes and phases of the vibration at several points on the BM were obtained from the finite-element model by applying sound pressure. These values were fed into the ionic current model, and changes in membrane potential and calcium ion concentration of the IHCs were calculated. The membrane potential of the IHC at the maximum amplitude point (CF point) was higher than that at the non-CF points. The calcium ion concentration at the CF point was also higher than that at the non-CF points. These results suggest that the cochlea achieves its good frequency discrimination ability through mechano-electrical transduction.

Label-free biosensing with functionalized nanopipette probes.

PubMed

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W; Pourmand, Nader

2009-03-24

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research.

In silico free energy predictions for ionic liquid-assisted exfoliation of a graphene bilayer into individual graphene nanosheets.

PubMed

Kamath, Ganesh; Baker, Gary A

2012-06-14

Free energies for graphene exfoliation from bilayer graphene using ionic liquids based on various cations paired with the bis(trifluoromethylsulfonyl)imide anion were determined from adaptive bias force-molecular dynamics (ABF-MD) simulation and fall in excellent qualitative agreement with experiment. This method has notable potential as an a priori screening tool for performance based rank order prediction of novel ionic liquids for the dispersion and exfoliation of various nanocarbons and inorganic graphene analogues.

Ionic liquids for addressing unmet needs in healthcare

PubMed Central

Agatemor, Christian; Ibsen, Kelly N.; Tanner, Eden E. L.

2018-01-01

Abstract Advances in the field of ionic liquids have opened new applications beyond their traditional use as solvents into other fields especially healthcare. The broad chemical space, rich with structurally diverse ions, and coupled with the flexibility to form complementary ion pairs enables task‐specific optimization at the molecular level to design ionic liquids for envisioned functions. Consequently, ionic liquids now are tailored as innovative solutions to address many problems in medicine. To date, ionic liquids have been designed to promote dissolution of poorly soluble drugs and disrupt physiological barriers to transport drugs to targeted sites. Also, their antimicrobial activity has been demonstrated and could be exploited to prevent and treat infectious diseases. Metal‐containing ionic liquids have also been designed and offer unique features due to incorporation of metals. Here, we review application‐driven investigations of ionic liquids in medicine with respect to current status and future potential. PMID:29376130

Regularity of beating of small clusters of embryonic chick ventricular heart-cells: experiment vs. stochastic single-channel population model

NASA Astrophysics Data System (ADS)

Krogh-Madsen, Trine; Kold Taylor, Louise; Skriver, Anne D.; Schaffer, Peter; Guevara, Michael R.

2017-09-01

The transmembrane potential is recorded from small isopotential clusters of 2-4 embryonic chick ventricular cells spontaneously generating action potentials. We analyze the cycle-to-cycle fluctuations in the time between successive action potentials (the interbeat interval or IBI). We also convert an existing model of electrical activity in the cluster, which is formulated as a Hodgkin-Huxley-like deterministic system of nonlinear ordinary differential equations describing five individual ionic currents, into a stochastic model consisting of a population of ˜20 000 independently and randomly gating ionic channels, with the randomness being set by a real physical stochastic process (radio static). This stochastic model, implemented using the Clay-DeFelice algorithm, reproduces the fluctuations seen experimentally: e.g., the coefficient of variation (standard deviation/mean) of IBI is 4.3% in the model vs. the 3.9% average value of the 17 clusters studied. The model also replicates all but one of several other quantitative measures of the experimental results, including the power spectrum and correlation integral of the voltage, as well as the histogram, Poincaré plot, serial correlation coefficients, power spectrum, detrended fluctuation analysis, approximate entropy, and sample entropy of IBI. The channel noise from one particular ionic current (IKs), which has channel kinetics that are relatively slow compared to that of the other currents, makes the major contribution to the fluctuations in IBI. Reproduction of the experimental coefficient of variation of IBI by adding a Gaussian white noise-current into the deterministic model necessitates using an unrealistically high noise-current amplitude. Indeed, a major implication of the modelling results is that, given the wide range of time-scales over which the various species of channels open and close, only a cell-specific stochastic model that is formulated taking into consideration the widely different ranges in the frequency content of the channel-noise produced by the opening and closing of several different types of channels will be able to reproduce precisely the various effects due to membrane noise seen in a particular electrophysiological preparation.

Programmable Hydrogel Ionic Circuits for Biologically Matched Electronic Interfaces.

PubMed

Zhao, Siwei; Tseng, Peter; Grasman, Jonathan; Wang, Yu; Li, Wenyi; Napier, Bradley; Yavuz, Burcin; Chen, Ying; Howell, Laurel; Rincon, Javier; Omenetto, Fiorenzo G; Kaplan, David L

2018-06-01

The increased need for wearable and implantable medical devices has driven the demand for electronics that interface with living systems. Current bioelectronic systems have not fully resolved mismatches between engineered circuits and biological systems, including the resulting pain and damage to biological tissues. Here, salt/poly(ethylene glycol) (PEG) aqueous two-phase systems are utilized to generate programmable hydrogel ionic circuits. High-conductivity salt-solution patterns are stably encapsulated within PEG hydrogel matrices using salt/PEG phase separation, which route ionic current with high resolution and enable localized delivery of electrical stimulation. This strategy allows designer electronics that match biological systems, including transparency, stretchability, complete aqueous-based connective interface, distribution of ionic electrical signals between engineered and biological systems, and avoidance of tissue damage from electrical stimulation. The potential of such systems is demonstrated by generating light-emitting diode (LED)-based displays, skin-mounted electronics, and stimulators that deliver localized current to in vitro neuron cultures and muscles in vivo with reduced adverse effects. Such electronic platforms may form the basis of future biointegrated electronic systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of glycine and current density on the mechanism of electrodeposition, composition and properties of Ni-Mn films prepared in ionic liquid

NASA Astrophysics Data System (ADS)

Guo, Jiacheng; Guo, Xingwu; Wang, Shaohua; Zhang, Zhicheng; Dong, Jie; Peng, Liming; Ding, Wenjiang

2016-03-01

The effects of glycine on the mechanism of electrodeposition of Ni-Mn alloy film prepared in ChCl-urea ionic liquid were studied in order to control the composition, microstructure and properties of the film. The cyclic voltammograms revealed that the presence of glycine in the ionic liquid can inhibit the reduction of Ni2+ ions but promote the reduction of Mn2+ ions in the cathodic scan. However, it promoted the dissolution of both Ni and Mn deposits in the ChCl-urea ionic liquids during the reverse scan. Glycine changed the mode of Ni-Mn film growth from Volmer-Weber mode into Stranski-Krastanov mode. The Mn content in the Ni-Mn film increased with the increase of concentration of glycine and current density. The Ni-Mn alloy film with 3.1 at.% Mn exhibited the lowest corrosion current density of 3 × 10-7 A/cm2 compared with other films prepared and exhibited better corrosion resistance than pure Ni film in 3.5 wt.% NaCl solution.

Reaching the Ionic Current Detection Limit in Silicon-Based Nanopores

NASA Astrophysics Data System (ADS)

Puster, Matthew; Rodriguez-Manzo, Julio Alejandro; Nicolai, Adrien; Meunier, Vincent; Drndic, Marija

2015-03-01

Solid-state nanopores act as single-molecule sensors whereby passage of an individual molecule in aqueous electrolyte through a nanopore is registered as a change in ionic conductance (ΔG). Future nanopore applications such as DNA sequencing at high bandwidth require high ΔG for optimal signal-to-noise ratio. Reducing the nanopore diameter and thickness increase ΔG. Molecule size limits the diameter, thus efforts concentrate on minimizing the thickness by thinning oxide/nitride films or using 2D materials. Weighted by electrolyte conductivity the highest ΔG reported to date for DNA translocations were obtained with nanopores made in oxide/nitride films. We present a controlled electron irradiation technique to thin such films to the limit of their stability, producing nanopores tailored to molecule size in amorphous Si with thicknesses less than 2 nm. We compare ΔG values with results found in the literature for DNA translocation through these nanopores, where access resistance becomes comparable to the resistance through the nanopore itself.

Mathematical modeling of electrical activity of uterine muscle cells.

PubMed

Rihana, Sandy; Terrien, Jeremy; Germain, Guy; Marque, Catherine

2009-06-01

The uterine electrical activity is an efficient parameter to study the uterine contractility. In order to understand the ionic mechanisms responsible for its generation, we aimed at building a mathematical model of the uterine cell electrical activity based upon the physiological mechanisms. First, based on the voltage clamp experiments found in the literature, we focus on the principal ionic channels and their cognate currents involved in the generation of this electrical activity. Second, we provide the methodology of formulations of uterine ionic currents derived from a wide range of electrophysiological data. The model is validated step by step by comparing simulated voltage-clamp results with the experimental ones. The model reproduces successfully the generation of single spikes or trains of action potentials that fit with the experimental data. It allows analyzing ionic channels implications. Likewise, the calcium-dependent conductance influences significantly the cellular oscillatory behavior.

Impact of ionic current variability on human ventricular cellular electrophysiology.

PubMed

Romero, Lucía; Pueyo, Esther; Fink, Martin; Rodríguez, Blanca

2009-10-01

Abnormalities in repolarization and its rate dependence are known to be related to increased proarrhythmic risk. A number of repolarization-related electrophysiological properties are commonly used as preclinical biomarkers of arrhythmic risk. However, the variability and complexity of repolarization mechanisms make the use of cellular biomarkers to predict arrhythmic risk preclinically challenging. Our goal is to investigate the role of ionic current properties and their variability in modulating cellular biomarkers of arrhythmic risk to improve risk stratification and identification in humans. A systematic investigation into the sensitivity of the main preclinical biomarkers of arrhythmic risk to changes in ionic current conductances and kinetics was performed using computer simulations. Four stimulation protocols were applied to the ten Tusscher and Panfilov human ventricular model to quantify the impact of +/-15 and +/-30% variations in key model parameters on action potential (AP) properties, Ca(2+) and Na(+) dynamics, and their rate dependence. Simulations show that, in humans, AP duration is moderately sensitive to changes in all repolarization current conductances and in L-type Ca(2+) current (I(CaL)) and slow component of the delayed rectifier current (I(Ks)) inactivation kinetics. AP triangulation, however, is strongly dependent only on inward rectifier K(+) current (I(K1)) and delayed rectifier current (I(Kr)) conductances. Furthermore, AP rate dependence (i.e., AP duration rate adaptation and restitution properties) and intracellular Ca(2+) and Na(+) levels are highly sensitive to both I(CaL) and Na(+)/K(+) pump current (I(NaK)) properties. This study provides quantitative insights into the sensitivity of preclinical biomarkers of arrhythmic risk to variations in ionic current properties in humans. The results show the importance of sensitivity analysis as a powerful method for the in-depth validation of mathematical models in cardiac electrophysiology.

Conductance of Ion Channels - Theory vs. Experiment

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael; Mijajlovic, Milan

2013-01-01

Transmembrane ion channels mediate a number of essential physiological processes in a cell ranging from regulating osmotic pressure to transmission of neural signals. Kinetics and selectivity of ion transport is of critical importance to a cell and, not surprisingly, it is a subject of numerous experimental and theoretical studies. In this presentation we will analyze in detail computer simulations of two simple channels from fungi - antiamoebin and trichotoxin. Each of these channels is made of an alpha-helical bundle of small, nongenomically synthesized peptides containing a number of rare amino acids and exhibits strong antimicrobial activity. We will focus on calculating ionic conductance defined as the ratio of ionic current through the channel to applied voltage. From molecular dynamics simulations, conductance can be calculated in at least two ways, each involving different approximations. Specifically, the current, given as the number of charges transferred through the channel per unit of time, can be obtained from the number of events in which ions cross the channel during the simulation. This method works well for large currents (high conductance values and/or applied voltages). If the number of crossing events is small, reliable estimates of current are difficult to achieve. Alternatively, conductance can be estimated assuming that ion transport can be well approximated as diffusion in the external potential given by the free energy profile. Then, the current can be calculated by solving the one-dimensional diffusion equation in this external potential and applied voltage (the generalized Nernst-Planck equation). To do so three ingredients are needed: the free energy profile, the position-dependent diffusion coefficient and the diffusive flux of ions into the channel. All these quantities can be obtained from molecular dynamics simulations. An important advantage of this method is that it can be used equally well to estimating large and small currents. In addition, once the free energy profile becomes available the full current-voltage dependence can be readily obtained. For both channels we carried out calculations using both approaches. We also tested the main assumptions underlying the diffusive model, such as uncorrelated nature of individual crossing events and Fickian diffusion. The accuracy and consistency of different methods will be discussed. Finally we will discuss how comparisons between calculated and measured ionic conductance and selectivity of transport can be used for determining structural models of the channels.

Influence of Electrical and Ionic Conductivities of Organic Electronic Ion Pump on Acetylcholine Exchange Performance

PubMed Central

Abdullayeva, Nazrin; Sankir, Mehmet

2017-01-01

By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future. PMID:28772946

Label-free biosensing with functionalized nanopipette probes

PubMed Central

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W.; Pourmand, Nader

2009-01-01

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research. PMID:19264962

The Na+/K+ pump is an important modulator of refractoriness and rotor dynamics in human atrial tissue.

PubMed

Sánchez, Carlos; Corrias, Alberto; Bueno-Orovio, Alfonso; Davies, Mark; Swinton, Jonathan; Jacobson, Ingemar; Laguna, Pablo; Pueyo, Esther; Rodríguez, Blanca

2012-03-01

Pharmacological treatment of atrial fibrillation (AF) exhibits limited efficacy. Further developments require a comprehensive characterization of ionic modulators of electrophysiology in human atria. Our aim is to systematically investigate the relative importance of ionic properties in modulating excitability, refractoriness, and rotor dynamics in human atria before and after AF-related electrical remodeling (AFER). Computer simulations of single cell and tissue atrial electrophysiology were conducted using two human atrial action potential (AP) models. Changes in AP, refractory period (RP), conduction velocity (CV), and rotor dynamics caused by alterations in key properties of all atrial ionic currents were characterized before and after AFER. Results show that the investigated human atrial electrophysiological properties are primarily modulated by maximal value of Na(+)/K(+) pump current (G(NaK)) as well as conductances of inward rectifier potassium current (G(K1)) and fast inward sodium current (G(Na)). G(NaK) plays a fundamental role through both electrogenic and homeostatic modulation of AP duration (APD), APD restitution, RP, and reentrant dominant frequency (DF). G(K1) controls DF through modulation of AP, APD restitution, RP, and CV. G(Na) is key in determining DF through alteration of CV and RP, particularly in AFER. Changes in ionic currents have qualitatively similar effects in control and AFER, but effects are smaller in AFER. The systematic analysis conducted in this study unravels the important role of the Na(+)/K(+) pump current in determining human atrial electrophysiology.

Computational solvation analysis of biomolecules in aqueous ionic liquid mixtures : From large flexible proteins to small rigid drugs.

PubMed

Zeindlhofer, Veronika; Schröder, Christian

2018-06-01

Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.

Ionic components of electric current at rat corneal wounds.

PubMed

Vieira, Ana Carolina; Reid, Brian; Cao, Lin; Mannis, Mark J; Schwab, Ivan R; Zhao, Min

2011-02-25

Endogenous electric fields and currents occur naturally at wounds and are a strong signal guiding cell migration into the wound to promote healing. Many cells involved in wound healing respond to small physiological electric fields in vitro. It has long been assumed that wound electric fields are produced by passive ion leakage from damaged tissue. Could these fields be actively maintained and regulated as an active wound response? What are the molecular, ionic and cellular mechanisms underlying the wound electric currents? Using rat cornea wounds as a model, we measured the dynamic timecourses of individual ion fluxes with ion-selective probes. We also examined chloride channel expression before and after wounding. After wounding, Ca(2+) efflux increased steadily whereas K(+) showed an initial large efflux which rapidly decreased. Surprisingly, Na(+) flux at wounds was inward. A most significant observation was a persistent large influx of Cl(-), which had a time course similar to the net wound electric currents we have measured previously. Fixation of the tissues abolished ion fluxes. Pharmacological agents which stimulate ion transport significantly increased flux of Cl(-), Na(+) and K(+). Injury to the cornea caused significant changes in distribution and expression of Cl(-) channel CLC2. These data suggest that the outward electric currents occurring naturally at corneal wounds are carried mainly by a large influx of chloride ions, and in part by effluxes of calcium and potassium ions. Ca(2+) and Cl(-) fluxes appear to be mainly actively regulated, while K(+) flux appears to be largely due to leakage. The dynamic changes of electric currents and specific ion fluxes after wounding suggest that electrical signaling is an active response to injury and offers potential novel approaches to modulate wound healing, for example eye-drops targeting ion transport to aid in the challenging management of non-healing corneal ulcers.

Influence of the ionic liquid/gas surface on ionic liquid chemistry.

PubMed

Lovelock, Kevin R J

2012-04-21

Applications such as gas storage, gas separation, NP synthesis and supported ionic liquid phase catalysis depend upon the interaction of different species with the ionic liquid/gas surface. Consequently, these applications cannot proceed to the full extent of their potential without a profound understanding of the surface structure and properties. As a whole, this perspective contains more questions than answers, which demonstrates the current state of the field. Throughout this perspective, crucial questions are posed and a roadmap is proposed to answer these questions. A critical analysis is made of the field of ionic liquid/gas surface structure and properties, and a number of design rules are mined. The effects of ionic additives on the ionic liquid/gas surface structure are presented. A possible driving force for surface formation is discussed that has, to the best of my knowledge, not been postulated in the literature to date. This driving force suggests that for systems composed solely of ions, the rules for surface formation of dilute electrolytes do not apply. The interaction of neutral additives with the ionic liquid/gas surface is discussed. Particular attention is focussed upon H(2)O and CO(2), vital additives for many applications of ionic liquids. Correlations between ionic liquid/gas surface structure and properties, ionic liquid surfaces plus additives, and ionic liquid applications are given. This journal is © the Owner Societies 2012

Thermoelectric Generators Based on Ionic Liquids

NASA Astrophysics Data System (ADS)

Laux, Edith; Uhl, Stefanie; Jeandupeux, Laure; López, Pilar Pérez; Sanglard, Pauline; Vanoli, Ennio; Marti, Roger; Keppner, Herbert

2018-03-01

Looking at energy harvesting using body or waste heat for portable electronic or on-board devices, Ionic liquids are interesting candidates as thermoactive materials in thermoelectric generators (TEGs) because of their outstanding properties. Two different kinds of ionic liquid, with alkylammonium and choline as cations, were studied, whereby different anions and redox couples were combined. This study focussed on the intention to find non-hazardous and environmentally friendly ionic liquids for TEGs to be selected among the thousands that can potentially be used. Seebeck coefficients (SEs) as high as - 15 mV/K were measured, in a particular case for an electrode temperature difference of 20 K. The bottleneck of our TEG device is still the abundance of negative SE liquids matching the internal resistance with the existing positive SE-liquids at series connections. In this paper, we show further progress in finding increased negative SE liquids. For current extraction from the TEG, the ionic liquid must be blended with a redox couple, allowing carrier exchange in a cyclic process under a voltage which is incuced by the asymmetry of the generator in terms of hot and cold electrodes. In our study, two types of redox pairs were tested. It was observed that a high SE of an ionic liquid/redox blend is not a sufficient condition for high power output. It appears that more complex effects between the ionic liquid and the electrode determine the magnitude of the final current/power output. The physico-chemical understanding of such a TEG cell is not yet available.

Thermoelectric Generators Based on Ionic Liquids

NASA Astrophysics Data System (ADS)

Laux, Edith; Uhl, Stefanie; Jeandupeux, Laure; López, Pilar Pérez; Sanglard, Pauline; Vanoli, Ennio; Marti, Roger; Keppner, Herbert

2018-06-01

Looking at energy harvesting using body or waste heat for portable electronic or on-board devices, Ionic liquids are interesting candidates as thermoactive materials in thermoelectric generators (TEGs) because of their outstanding properties. Two different kinds of ionic liquid, with alkylammonium and choline as cations, were studied, whereby different anions and redox couples were combined. This study focussed on the intention to find non-hazardous and environmentally friendly ionic liquids for TEGs to be selected among the thousands that can potentially be used. Seebeck coefficients (SEs) as high as - 15 mV/K were measured, in a particular case for an electrode temperature difference of 20 K. The bottleneck of our TEG device is still the abundance of negative SE liquids matching the internal resistance with the existing positive SE-liquids at series connections. In this paper, we show further progress in finding increased negative SE liquids. For current extraction from the TEG, the ionic liquid must be blended with a redox couple, allowing carrier exchange in a cyclic process under a voltage which is incuced by the asymmetry of the generator in terms of hot and cold electrodes. In our study, two types of redox pairs were tested. It was observed that a high SE of an ionic liquid/redox blend is not a sufficient condition for high power output. It appears that more complex effects between the ionic liquid and the electrode determine the magnitude of the final current/power output. The physico-chemical understanding of such a TEG cell is not yet available.

Limitations in electrophysiological model development and validation caused by differences between simulations and experimental protocols.

PubMed

Carro, Jesús; Rodríguez-Matas, José F; Monasterio, Violeta; Pueyo, Esther

2017-10-01

Models of ion channel dynamics are usually built by fitting isolated cell experimental values of individual parameters while neglecting the interaction between them. Another shortcoming regards the estimation of ionic current conductances, which is often based on quantification of Action Potential (AP)-derived markers. Although this procedure reduces the uncertainty in the calculation of conductances, many studies evaluate electrophysiological AP-derived markers from single cell simulations, whereas experimental measurements are obtained from tissue preparations. In this work, we explore the limitations of these approaches to estimate ion channel dynamics and maximum current conductances and how they could be overcome by using multiscale simulations of experimental protocols. Four human ventricular cell models, namely ten Tusscher and Panfilov (2006), Grandi et al. (2010), O'Hara et al. (2011), and Carro et al. (2011), were used. Two problems involving scales from ion channels to tissue were investigated: 1) characterization of L-type calcium voltage-dependent inactivation I Ca,L ; 2) identification of major ionic conductance contributors to steady-state AP markers, including APD 90 , APD 75 , APD 50 , APD 25 , Triangulation and maximal and minimal values of V and dV/dt during the AP (V max , V min , dV/dt max , dV/dt min ). Our results show that: 1) I Ca,L inactivation characteristics differed significantly when calculated from model equations and from simulations reproducing the experimental protocols. 2) Large differences were found in the ionic currents contributors to APD 25 , Triangulation, V max , dV/dt max and dV/dt min between single cells and 1D-tissue. When proposing any new model formulation, or evaluating an existing model, consistency between simulated and experimental data should be verified considering all involved effects and scales. Copyright © 2016 Elsevier Ltd. All rights reserved.

The radiation chemistry of ionic liquids: A review

DOE PAGES

Mincher, Bruce J.; Wishart, James F.

2014-07-03

Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Voltage dependence of a stochastic model of activation of an alpha helical S4 sensor in a K channel membrane

NASA Astrophysics Data System (ADS)

Vaccaro, S. R.

2011-09-01

The voltage dependence of the ionic and gating currents of a K channel is dependent on the activation barriers of a voltage sensor with a potential function which may be derived from the principal electrostatic forces on an S4 segment in an inhomogeneous dielectric medium. By variation of the parameters of a voltage-sensing domain model, consistent with x-ray structures and biophysical data, the lowest frequency of the survival probability of each stationary state derived from a solution of the Smoluchowski equation provides a good fit to the voltage dependence of the slowest time constant of the ionic current in a depolarized membrane, and the gating current exhibits a rising phase that precedes an exponential relaxation. For each depolarizing potential, the calculated time dependence of the survival probabilities of the closed states of an alpha helical S4 sensor are in accord with an empirical model of the ionic and gating currents recorded during the activation process.

Enhancement of Force Generated by Individual Myosin Heads in Skinned Rabbit Psoas Muscle Fibers at Low Ionic Strength

PubMed Central

Sugi, Haruo; Abe, Takahiro; Kobayashi, Takakazu; Chaen, Shigeru; Ohnuki, Yoshiki; Saeki, Yasutake; Sugiura, Seiryo

2013-01-01

Although evidence has been presented that, at low ionic strength, myosin heads in relaxed skeletal muscle fibers form linkages with actin filaments, the effect of low ionic strength on contraction characteristics of Ca2+-activated muscle fibers has not yet been studied in detail. To give information about the mechanism of muscle contraction, we have examined the effect of low ionic strength on the mechanical properties and the contraction characteristics of skinned rabbit psoas muscle fibers in both relaxed and maximally Ca2+-activated states. By progressively decreasing KCl concentration from 125 mM to 0 mM (corresponding to a decrease in ionic strength μ from 170 mM to 50 mM), relaxed fibers showed changes in mechanical response to sinusoidal length changes and ramp stretches, which are consistent with the idea of actin-myosin linkage formation at low ionic strength. In maximally Ca2+-activated fibers, on the other hand, the maximum isometric force increased about twofold by reducing KCl concentration from 125 to 0 mM. Unexpectedly, determination of the force-velocity curves indicated that, the maximum unloaded shortening velocity Vmax, remained unchanged at low ionic strength. This finding indicates that the actin-myosin linkages, which has been detected in relaxed fibers at low ionic strength, are broken quickly on Ca2+ activation, so that the linkages in relaxed fibers no longer provide any internal resistance against fiber shortening. The force-velocity curves, obtained at various levels of steady Ca2+-activated isometric force, were found to be identical if they are normalized with respect to the maximum isometric force. The MgATPase activity of muscle fibers during isometric force generation was found not to change appreciably at low ionic strength despite the two-fold increase in Ca2+-activated isometric force. These results can be explained in terms of enhancement of force generated by individual myosin heads, but not by any changes in kinetic properties of cyclic actin-myosin interaction. PMID:23691080

The ionic bases of the action potential in isolated mouse cardiac Purkinje cell.

PubMed

Vaidyanathan, Ravi; O'Connell, Ryan P; Deo, Makarand; Milstein, Michelle L; Furspan, Philip; Herron, Todd J; Pandit, Sandeep V; Musa, Hassan; Berenfeld, Omer; Jalife, José; Anumonwo, Justus M B

2013-01-01

Collecting electrophysiological and molecular data from the murine conduction system presents technical challenges. Thus, only little advantage has been taken of numerous genetically engineered murine models to study excitation through the cardiac conduction system of the mouse. To develop an approach for isolating murine cardiac Purkinje cells (PCs), to characterize major ionic currents and to use the data to simulate action potentials (APs) recorded from PCs. Light microscopy was used to isolate and identify PCs from apical and septal cells. Current and voltage clamp techniques were used to record APs and whole cell currents. We then simulated a PC AP on the basis of our experimental data. APs recorded from PCs were significantly longer than those recorded from ventricular cells. The prominent plateau phase of the PC AP was very negative (≈-40 mV). Spontaneous activity was observed only in PCs. The inward rectifier current demonstrated no significant differences compared to ventricular myocytes (VMs). However, sodium current density was larger, and the voltage-gated potassium current density was significantly less in PCs compared with myocytes. T-type Ca(2+) currents (I(Ca,T)) were present in PCs but not VMs. Computer simulations suggest that I(Ca,T) and cytosolic calcium diffusion significantly modulate AP profile recorded in PCs, as compared to VMs. Our study provides the first comprehensive ionic profile of murine PCs. The data show unique features of PC ionic mechanisms that govern its excitation process. Experimental data and numerical modeling results suggest that a smaller voltage-gated potassium current and the presence of I(Ca,T) are important determinants of the longer and relatively negative plateau phase of the APs. Copyright © 2013 Heart Rhythm Society. Published by Elsevier Inc. All rights reserved.

Weakening of ion-channel interactions of Na+ and Li+ in acetylcholine-receptor channels of frog skeletal muscle with an increase in agonist concentration.

PubMed

Manthey, A A

1998-05-01

The possibility that increases in agonist concentration beyond threshold levels may force changes in the character of high-conductance open states of skeletal muscle nicotinic acetylcholine receptor channels (nAChR) was examined by seeing whether differences in several critical ionic properties of nAChR currents could be detected with changes in agonist level. Single- and bi-ionic whole-cell currents of Na+ and Li+ in voltage-clamped frog (Rana pipiens) muscle fibers were measured during local superfusion of endplates with carbamylcholine (carb) at concentrations of 54 microm (low-carb) and 270 microM (high-carb). Three ionic properties that would be affected by changes in the open-state configuration of channel subunits were tested. First, ion-saturation characteristics. Peak Na+ and Li+ currents in low-carb trials showed sublinear dependence on ion concentrations from 0 to 60 mM with Km values of 78 (Na+) and 49 (Li+) mM and a power function slope of 0. 75 on double-log plot. In contrast, the concentration dependence of Na+ and Li+ currents in high-carb tests was linear through the origin with a power function slope of 1.02. Second, Na+/Li+ selectivity. The ratio of peak Na+ and Li+ currents in low-carb tests varied from 1.86 to 2.28 for ion concentrations of from 20 to 60 mM [mean = 2.02 +/- 0.06 (SEM)] whereas the ratio for high-carb trials ranged from only 1.29 to 1.52 [mean = 1.42 +/- 0.40 (SEM)]. Third, competitive interactions of Na+ and Li+ currents. Equimolar mixtures of Na+ and Li+ in low-carb tests produced bi-ionic inward currents which were never larger than the single-ion Na+ current alone, but bi-ionic currents at the high-carb level were always greater than the single-ion Na+ current, approximating the sum of the single-ion Na+ and Li+ currents in most cases. The results are consistent with a decrease in ion-channel binding at the high-carb level and support the possibility of agonist-induced changes in the high-conductance open-state configuration of nAChR subunits which result in a weakening of constraints on cation movements through the channel.

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid-modified materials for solid-phase extraction and separation: a review.

PubMed

Vidal, Lorena; Riekkola, Marja-Liisa; Canals, Antonio

2012-02-17

In recent years, materials science has propelled to the research forefront. Ionic liquids with unique and fascinating properties have also left their footprints to the developments of materials science during the last years. In this review we highlight some of their recent advances and provide an overview at the current status of ionic liquid-modified materials applied in solid-phase extraction, liquid and gas chromatography and capillary electrochromatography with reference to recent applications. In addition, the potential of ionic liquids in the modification of capillary inner wall in capillary electrophoresis is demonstrated. The main target material modified with ionic liquids is silica, but polymers and monoliths have recently joined the studies. Although imidazolium is still clearly the most commonly used ionic liquid for the covalently modification of materials, the exploitation of pyridinium and phosphonium will most probably increase in the future. Copyright © 2011 Elsevier B.V. All rights reserved.

Ab-Initio analysis of TlBr: limiting the ionic current without degrading the electronic one

NASA Astrophysics Data System (ADS)

Rocha Leao, Cedric; Lordi, Vincenzo

2011-03-01

Although TlBr in principle presents all the theoretical requirements for making high resolution room temperature radiation detectors, practical applications of TlBr have proven to be nonviable due to the polarization that is observed in the crystal after relatively short periods of operation. This polarization, that is believed to be caused by accumulation of oppositely charged ionic species at the ends of the crystal, results in an electric field that opposes that of the applied bias, counter-acting its effect. In this work, we use state of the art quantum modeling to benchmark the theoretical limits for the performance of TlBr as a radiation detector, showing that the best experimental reports demonstrate near-ideal electronic characteristics. We then propose a model to inhibit the detrimental ionic current in the material without impacting the excellent properties of the electronic current. Prepared by LLNL under Contract DE-AC52-07NA27344.

Geometrical control of ionic current rectification in a configurable nanofluidic diode.

PubMed

Alibakhshi, Mohammad Amin; Liu, Binqi; Xu, Zhiping; Duan, Chuanhua

2016-09-01

Control of ionic current in a nanofluidic system and development of the elements analogous to electrical circuits have been the subject of theoretical and experimental investigations over the past decade. Here, we theoretically and experimentally explore a new technique for rectification of ionic current using asymmetric 2D nanochannels. These nanochannels have a rectangular cross section and a stepped structure consisting of a shallow and a deep side. Control of height and length of each side enables us to obtain optimum rectification at each ionic strength. A 1D model based on the Poisson-Nernst-Planck equation is derived and validated against the full 2D numerical solution, and a nondimensional concentration is presented as a function of nanochannel dimensions, surface charge, and the electrolyte concentration that summarizes the rectification behavior of such geometries. The rectification factor reaches a maximum at certain electrolyte concentration predicted by this nondimensional number and decays away from it. This method of fabrication and control of a nanofluidic diode does not require modification of the surface charge and facilitates the integration with lab-on-a-chip fluidic circuits. Experimental results obtained from the stepped nanochannels are in good agreement with the 1D theoretical model.

The effect of humidity on ionic wind velocity in ambient air

NASA Astrophysics Data System (ADS)

Chen, She; Nobelen, J. C. P. Y.; Nijdam, S.

2016-09-01

Due to the evolution of portable electronics and LED lightning system, advances in air cooling technologies must also keep pace. Active cooling by ionic wind, which is usually generated by corona discharge, can greatly reduce the noise and lifetime issues compared to the mechanical fans. The wind is induced when a gas discharge is formed, and neutral molecules gain their energy by the momentum transfer of ion-neutral collisions. However, there is few discussion about the effect of gas composition such as humidity on the wind generation and the physical mechanism is not clear. In the experiment, a positive 5-20 kV DC voltage is applied to the needle-cylinder electrodes with separation of 20 mm. The ionic wind velocity is measured by hot wire anemometry. As the relative humidity (RH) in the ambient air increases, the velocity is found to be severely inhibited. The current is also measured between the cylinder electrode and earth. The results show that the DC component of corona current decreases when RH increases. Since both the discharge current and the ion mobility are reduced when RH increases, their combined effects determine the ionic wind velocity. This work is supported by STW project 13651.

Comparison of Three Ionic Liquid-Tolerant Cellulases by Molecular Dynamics

PubMed Central

Jaeger, Vance; Burney, Patrick; Pfaendtner, Jim

2015-01-01

We have employed molecular dynamics to investigate the differences in ionic liquid tolerance among three distinct family 5 cellulases from Trichoderma viride, Thermogata maritima, and Pyrococcus horikoshii. Simulations of the three cellulases were conducted at a range of temperatures in various binary mixtures of the ionic liquid 1-ethyl-3-methyl-imidazolium acetate with water. Our analysis demonstrates that the effects of ionic liquids on the enzymes vary in each individual case from local structural disturbances to loss of much of one of the enzyme’s secondary structure. Enzymes with more negatively charged surfaces tend to resist destabilization by ionic liquids. Specific and unique structural changes in the enzymes are induced by the presence of ionic liquids. Disruption of the secondary structure, changes in dynamical motion, and local changes in the binding pocket are observed in less tolerant enzymes. Ionic-liquid-induced denaturation of one of the enzymes is indicated over the 500 ns timescale. In contrast, the most tolerant cellulase behaves similarly in water and in ionic-liquid-containing mixtures. Unlike the heuristic approaches that attempt to predict enzyme stability using macroscopic properties, molecular dynamics allows us to predict specific atomic-level structural and dynamical changes in an enzyme’s behavior induced by ionic liquids and other mixed solvents. Using these insights, we propose specific experimentally testable hypotheses regarding the origin of activity loss for each of the systems investigated in this study. PMID:25692593

Real-space analysis of diffusion behavior and activation energy of individual monatomic ions in a liquid.

PubMed

Miyata, Tomohiro; Uesugi, Fumihiko; Mizoguchi, Teruyasu

2017-12-01

Investigation of the local dynamic behavior of atoms and molecules in liquids is crucial for revealing the origin of macroscopic liquid properties. Therefore, direct imaging of single atoms to understand their motions in liquids is desirable. Ionic liquids have been studied for various applications, in which they are used as electrolytes or solvents. However, atomic-scale diffusion and relaxation processes in ionic liquids have never been observed experimentally. We directly observe the motion of individual monatomic ions in an ionic liquid using scanning transmission electron microscopy (STEM) and reveal that the ions diffuse by a cage-jump mechanism. Moreover, we estimate the diffusion coefficient and activation energy for the diffusive jumps from the STEM images, which connect the atomic-scale dynamics to macroscopic liquid properties. Our method is the only available means to observe the motion, reactions, and energy barriers of atoms/molecules in liquids.

Electroosmotic flow hysteresis for dissimilar ionic solutions

PubMed Central

Lim, An Eng; Lam, Yee Cheong

2015-01-01

Electroosmotic flow (EOF) with two or more fluids is commonly encountered in various microfluidics applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during the displacement flow of solutions with dissimilar ionic species. In this investigation, electroosmotic displacement flow involving dissimilar ionic solutions was studied experimentally through a current monitoring method and numerically through finite element simulations. The flow hysteresis can be characterized by the turning and displacement times; turning time refers to the abrupt gradient change of current-time curve while displacement time is the time for one solution to completely displace the other solution. Both experimental and simulation results illustrate that the turning and displacement times for a particular solution pair can be directional-dependent, indicating that the flow conditions in the microchannel are not the same in the two different flow directions. The mechanics of EOF hysteresis was elucidated through the theoretical model which includes the ionic mobility of each species, a major governing parameter. Two distinct mechanics have been identified as the causes for the EOF hysteresis involving dissimilar ionic solutions: the widening/sharpening effect of interfacial region between the two solutions and the difference in ion concentration distributions (and thus average zeta potentials) in different flow directions. The outcome of this investigation contributes to the fundamental understanding of flow behavior in microfluidic systems involving solution pair with dissimilar ionic species. PMID:25945139

Multilevel Molecular Modeling Approach for a Rational Design of Ionic Current Sensors for Nanofluidics.

PubMed

Kirch, Alexsandro; de Almeida, James M; Miranda, Caetano R

2018-05-10

The complexity displayed by nanofluidic-based systems involves electronic and dynamic aspects occurring across different size and time scales. To properly model such kind of system, we introduced a top-down multilevel approach, combining molecular dynamics simulations (MD) with first-principles electronic transport calculations. The potential of this technique was demonstrated by investigating how the water and ionic flow through a (6,6) carbon nanotube (CNT) influences its electronic transport properties. We showed that the confinement on the CNT favors the partially hydrated Na, Cl, and Li ions to exchange charge with the nanotube. This leads to a change in the electronic transmittance, allowing for the distinguishing of cations from anions. Such an ionic trace may handle an indirect measurement of the ionic current that is recorded as a sensing output. With this case study, we are able to show the potential of this top-down multilevel approach, to be applied on the design of novel nanofluidic devices.

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids

NASA Astrophysics Data System (ADS)

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM). Electronic supplementary information (ESI) available: In situ image of PEDOT in [HMIm]FAP and in situ studies of PEDOT grown in [EMIm]TFSA and redox behavior of PEDOT. See DOI: 10.1039/c0nr00579g

Harnessing Poly(ionic liquid)s for Sensing Applications.

PubMed

Guterman, Ryan; Ambrogi, Martina; Yuan, Jiayin

2016-07-01

The interest in poly(ionic liquid)s for sensing applications is derived from their strong interactions to a variety of analytes. By combining the desirable mechanical properties of polymers with the physical and chemical properties of ILs, new materials can be created. The tunable nature of both ionic liquids and polymers allows for incredible diversity, which is exemplified in their broad applicability. In this article we examine the new field of poly(ionic liquid) sensors by providing a detailed look at the current state-of-the-art sensing devices for solvents, gases, biomolecules, pH, and anions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Signal and Noise in FET-Nanopore Devices.

PubMed

Parkin, William M; Drndić, Marija

2018-02-23

The combination of a nanopore with a local field-effect transistor (FET-nanopore), like a nanoribbon, nanotube, or nanowire, in order to sense single molecules translocating through the pore is promising for DNA sequencing at megahertz bandwidths. Previously, it was experimentally determined that the detection mechanism was due to local potential fluctuations that arise when an analyte enters a nanopore and constricts ion flow through it, rather than the theoretically proposed mechanism of direct charge coupling between the DNA and nanowire. However, there has been little discussion on the experimentally observed detection mechanism and its relation to the operation of real devices. We model the intrinsic signal and noise in such an FET-nanopore device and compare the results to the ionic current signal. The physical dimensions of DNA molecules limit the change in gate voltage on the FET to below 40 mV. We discuss the low-frequency flicker noise (<10 kHz), medium-frequency thermal noise (<100 kHz), and high-frequency capacitive noise (>100 kHz) in FET-nanopore devices. At bandwidths dominated by thermal noise, the signal-to-noise ratio in FET-nanopore devices is lower than in the ionic current signal. At high frequencies, where noise due to parasitic capacitances in the amplifier and chip is the dominant source of noise in ionic current measurements, high-transconductance FET-nanopore devices can outperform ionic current measurements.

Applications of Synthetic Microchannel and Nanopore Systems

NASA Astrophysics Data System (ADS)

Hinkle, Thomas Preston

This thesis describes research conducted on the physics and applications of micro- and nanoscale ion-conducting channels. Making use of the nanoscale physics that takes place in the vicinity of charged surfaces, there is the possibility that nanopores, holes on the order of 1 nm in size, could be used to make complex integrated ionic circuits. For inspiration on what such circuits could achieve we only need to look to biology systems, immensely complex machines that at their most basic level require precise control of ions and intercellular electric potentials to function. In order to contribute to the ever expanding field of nanopore research, we engineered novel hybrid insulator-conductor nanopores that behave analagously to ionic diodes, which allow passage of current flow in one direction but severely limit the current in the opposite direction. The experiments revealed that surface polarization of the conducting material can induce the formation of an electrical double layer in the same way static surface charges can. Furthermore, we showed that the hybrid device behaved similar to an ionic diode, and could see potential use as a standard rectifying element in ionic circuits. Another application based on ion conducting channels is resistive pulse sensing, a single particle detection and characterization method. We present three main experiments that expand the capacity of resistive pulse sensing for particle characterization. First, we demonstrate how resistive pulse sensing in pores with longitudinal irregularities can be used to measure the lengths of individual nanoparticles. Then, we describe an entirely new hybrid approach to resistive pulse sensing, whereby the electrical measurements are combined with simultaneous optical imaging. The hybrid method allows for validation of the resistive pulse signals and will greatly contribute to their interpretability. We present experiments that explore some of the possibilities of the hybrid method. Then, building off the hybrid method we present experiments performed to measure single particle deformability with resistive pulse sensing. Using a novel microfluidic channel design, we were able to reproducibily induce bidirectional deformation of cells. We describe how these deformations could be detected with the resistive pulse signal alone, paving the way for resistive pulse sensing based cell deformability cytometers.

[Diagnostic Significance of BAT in Anaphylaxis to Non-ionic Contrast Media].

PubMed

Zhang, Hao-yue; Xu, Su-jun; Tang, Xiao-xian; Niu, Ji-jun; Guo, Xiang-jie; Gao, Cai-rong

2015-06-01

To investigate the diagnostic significance of basophil activation test (BAT) in anaphylaxis to non-ionic contrast media through testing the content of CD63, mast cell-carboxypeptidase A3 (MC-CPA3), and terminal complement complex SC5b-9 of the individuals by testing their levels in the normal immune group and the anaphylaxis groups to β-lactam drugs and non -ionic contrast media. The CD63 expression of basophilic granulocyte in blood was detected by flow cytometry. The levels of MC-CPA3 in blood serum and SC5b-9 in blood plasma were detected by ELISA. The CD63 expression of basophilic granulocyte in blood, the levels of MC-CPA3 and SC5b-9 of anaphylaxis to non-ionic contrast media and β-lactam drugs were significantly higher than that in normal immune group (P < 0.05). There is activation of basophilic granulocytes, mast cells and complement system in anaphylaxis to non-ionic contrast media. BAT can be used to diagnose the anaphylaxis to non-ionic contrast media.

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Graphene nanopore devices for DNA sensing.

PubMed

Merchant, Chris A; Drndić, Marija

2012-01-01

We describe here a method for detecting the translocation of individual DNA molecules through nanopores created in graphene membranes. The devices consist of 1-5-nm thick graphene membranes with electron-beam sculpted nanopores from 5 to 10 nm in diameter. Due to the thin nature of the graphene membranes, and the reduced electrical resistance, we observe larger blocked currents than for traditional solid-state nanopores. We also show how ionic current noise levels can be reduced with the atomic-layer deposition of a few nanometers of titanium dioxide over the graphene surface. Unlike traditional solid-state nanopore materials that are insulating, graphene is an excellent electrical conductor, and its use opens the door to a new future class of nanopore devices in which electronic sensing and control is performed directly at the pore.

[Atomic/ionic fluorescence in microwave plasma torch discharge excited by high current microsecond pulsed hollow cathode lamp-europium atomic/ionic fluorescence spectrometry].

PubMed

Gong, Z; Liang, F; Yang, P; Jin, Q; Huang, B

1999-06-01

Eu atomic and ionic fluorescence spectrometry in microwave plasma torch discharge excited by high current microsecond pulsed hollow cathode lamp (HCMP HCL-MPT AFS/IFS) was studied. Operating conditions were optimized. The best detection limits for AFS and IFS obtained with a desolvated ultrasonic nebulization system were 42.0 ng/mL for Eu I 462.7 nm and 21.8 ng/mL for Eu II 381.97 nm, respectively, both were better than those given by the instruction manual of a Baird ICP AFS-2000 spectrometer using pneumatic concentric nebulizer with desolvation for AFS, but were significantly higher than those obtained by using the Baird spectrometer with a mini-monochromator and a ultrasonic nebulzer system.

Ionic liquids in tribology.

PubMed

Minami, Ichiro

2009-06-24

Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

Electromechanically generating electricity with a gapped-graphene electric generator

NASA Astrophysics Data System (ADS)

Dressen, Donald; Golovchenko, Jene

2015-03-01

We demonstrate the fabrication and operation of a gapped-graphene electric generator (G-GEG) device. The G-GEG generates electricity from the mechanical oscillation of droplets of electrolytes and ionic liquids. The spontaneous adsorption of ionic species on graphene charges opposing electric double-layer capacitors (EDLCs) on each half of the device. Modulating the area of contact between the droplet and graphene leads to adsorption/desorption of ions, effectively charging/discharging each EDLC and generating a current. The flow of current supports a potential difference across the G-GEG due to the device's internal impedance. Both the magnitude and polarity of the induced current and voltage show a strong dependence on the type of ionic species used, suggesting that certain ions interact more strongly with graphene than others. We find that a simple model circuit consisting of an AC current source in series with a resistor and a time-varying capacitor accurately predicts the device's dynamic behavior. Additionally, we discuss the effect of graphene's intrinsic quantum capacitance on the G-GEG's performance and speculate on the utility of the device in the context of energy harvesting.

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

Chen, Qing; Gerhardt, Michael R.; Aziz, Michael J.

We measure the polarization characteristics of a quinone-bromide redox flow battery with interdigitated flow fields, using electrochemical impedance spectroscopy and voltammetry of a full cell and of a half cell against a reference electrode. We find linear polarization behavior at 50% state of charge all the way to the short-circuit current density of 2.5 A/cm 2. We uniquely identify the polarization area-specific resistance (ASR) of each electrode, the membrane ASR to ionic current, and the electronic contact ASR. We use voltage probes to deduce the electronic current density through each sheet of carbon paper in the quinone-bearing electrode. By alsomore » interpreting the results using the Newman 1-D porous electrode model, we deduce the volumetric exchange current density of the porous electrode. We uniquely evaluate the power dissipation and identify a correspondence to the contributions to the electrode ASR from the faradaic, electronic, and ionic transport processes. We find that, within the electrode, more power is dissipated in the faradaic process than in the electronic and ionic conduction processes combined, despite the observed linear polarization behavior. We examine the sensitivity of the ASR to the values of the model parameters. The greatest performance improvement is anticipated from increasing the volumetric exchange current density.« less

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Voltage-Clamp Studies on Uterine Smooth Muscle

PubMed Central

Anderson, Nels C.

1969-01-01

These studies have developed and tested an experimental approach to the study of membrane ionic conductance mechanisms in strips of uterine smooth muscle. The experimental and theoretical basis for applying the double sucrose-gap technique is described along with the limitations of this system. Nonpropagating membrane action potentials were produced in response to depolarizing current pulses under current-clamp conditions. The stepwise change of membrane potential under voltage-clamp conditions resulted in a family of ionic currents with voltage- and time-dependent characteristics. In sodium-free solution the peak transient current decreased and its equilibrium potential shifted along the voltage axis toward a more negative internal potential. These studies indicate a sodium-dependent, regenerative excitation mechanism. PMID:5796366

Effect of pH on ion current through conical nanopores

NASA Astrophysics Data System (ADS)

Chander, M.; Kumar, R.; Kumar, S.; Kumar, N.

2018-05-01

Here, we examined ionic current behavior of conical nanopores at different pH and a fixed ion concentration of potassium halide (KCl). Conical shaped nanopores have been developed by chemical etching technique in polyethylene terephthalate (PET) membrane/foil of thickness 12 micron. For this we employed a self-assembled electrochemical cell having two chambers and the foil was fitted in the centre of cell. The nanopores were produced in the foil using etching and stopping solutions. The experimental results show that ionic current rectification (ICR) occurs through synthesized conical nanopores. Further, ion current increases significantly with increase of voltage from the base side of nanopores to the tip side at fixed pH of electrolyte.

Ionic Conductivity, Structural Deformation and Programmable Anisotropy of DNA Origami in Electric Field

PubMed Central

Li, Chen-Yu; Hemmig, Elisa A.; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia

2015-01-01

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules—a DNA origami plate— placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg2+ ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA. PMID:25623807

Ionic conductivity, structural deformation, and programmable anisotropy of DNA origami in electric field.

PubMed

Li, Chen-Yu; Hemmig, Elisa A; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia; Keyser, Ulrich F; Aksimentiev, Aleksei

2015-02-24

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules, a DNA origami plate, placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg(2+) ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA.

Refinement of current monitoring methodology for electroosmotic flow assessment under low ionic strength conditions

PubMed Central

Saucedo-Espinosa, Mario A.; Lapizco-Encinas, Blanca H.

2016-01-01

Current monitoring is a well-established technique for the characterization of electroosmotic (EO) flow in microfluidic devices. This method relies on monitoring the time response of the electric current when a test buffer solution is displaced by an auxiliary solution using EO flow. In this scheme, each solution has a different ionic concentration (and electric conductivity). The difference in the ionic concentration of the two solutions defines the dynamic time response of the electric current and, hence, the current signal to be measured: larger concentration differences result in larger measurable signals. A small concentration difference is needed, however, to avoid dispersion at the interface between the two solutions, which can result in undesired pressure-driven flow that conflicts with the EO flow. Additional challenges arise as the conductivity of the test solution decreases, leading to a reduced electric current signal that may be masked by noise during the measuring process, making for a difficult estimation of an accurate EO mobility. This contribution presents a new scheme for current monitoring that employs multiple channels arranged in parallel, producing an increase in the signal-to-noise ratio of the electric current to be measured and increasing the estimation accuracy. The use of this parallel approach is particularly useful in the estimation of the EO mobility in systems where low conductivity mediums are required, such as insulator based dielectrophoresis devices. PMID:27375813

Biological nanopore MspA for DNA sequencing

NASA Astrophysics Data System (ADS)

Manrao, Elizabeth A.

Unlocking the information hidden in the human genome provides insight into the inner workings of complex biological systems and can be used to greatly improve health-care. In order to allow for widespread sequencing, new technologies are required that provide fast and inexpensive readings of DNA. Nanopore sequencing is a third generation DNA sequencing technology that is currently being developed to fulfill this need. In nanopore sequencing, a voltage is applied across a small pore in an electrolyte solution and the resulting ionic current is recorded. When DNA passes through the channel, the ionic current is partially blocked. If the DNA bases uniquely modulate the ionic current flowing through the channel, the time trace of the current can be related to the sequence of DNA passing through the pore. There are two main challenges to realizing nanopore sequencing: identifying a pore with sensitivity to single nucleotides and controlling the translocation of DNA through the pore so that the small single nucleotide current signatures are distinguishable from background noise. In this dissertation, I explore the use of Mycobacterium smegmatis porin A (MspA) for nanopore sequencing. In order to determine MspA's sensitivity to single nucleotides, DNA strands of various compositions are held in the pore as the resulting ionic current is measured. DNA is immobilized in MspA by attaching it to a large molecule which acts as an anchor. This technique confirms the single nucleotide resolution of the pore and additionally shows that MspA is sensitive to epigenetic modifications and single nucleotide polymorphisms. The forces from the electric field within MspA, the effective charge of nucleotides, and elasticity of DNA are estimated using a Freely Jointed Chain model of single stranded DNA. These results offer insight into the interactions of DNA within the pore. With the nucleotide sensitivity of MspA confirmed, a method is introduced to controllably pass DNA through the pore. Using a DNA polymerase, DNA strands are stepped through MspA one nucleotide at a time. The steps are observable as distinct levels on the ionic-current time-trace and are related to the DNA sequence. These experiments overcome the two fundamental challenges to realizing MspA nanopore sequencing and pave the way to the development of a commercial technology.

Inverted battery design as ion generator for interfacing with biosystems

DOE PAGES

Wang, Chengwei; Fu, Kun; Dai, Jiaqi; ...

2017-07-24

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As amore » proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications« less

Inverted battery design as ion generator for interfacing with biosystems

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

Wang, Chengwei; Fu, Kun; Dai, Jiaqi

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As amore » proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications« less

Inverted battery design as ion generator for interfacing with biosystems

PubMed Central

Wang, Chengwei; Fu, Kun (Kelvin); Dai, Jiaqi; Lacey, Steven D.; Yao, Yonggang; Pastel, Glenn; Xu, Lisha; Zhang, Jianhua; Hu, Liangbing

2017-01-01

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As a proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications. PMID:28737174

UV-vis, IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet-oxytetracycline

NASA Astrophysics Data System (ADS)

Orellana, Sandra; Soto, César; Toral, M. Inés

2010-01-01

The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV-vis spectrophotometry, 1H NMR, measurement of relaxation times T1 and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV-OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.

Impact of gate geometry on ionic liquid gated ionotronic systems

DOE PAGES

Wong, Anthony T.; Noh, Joo Hyon; Pudasaini, Pushpa Raj; ...

2017-01-23

Ionic liquid electrolytes are gaining widespread application as a gate dielectric used to control ion transport in functional materials. This letter systematically examines the important influence that device geometry in standard “side gate” 3-terminal geometries plays in device performance of a well-known oxygen ion conductor. We show that the most influential component of device design is the ratio between the area of the gate electrode and the active channel, while the spacing between these components and their individual shapes has a negligible contribution. Finally, these findings provide much needed guidance in device design intended for ionotronic gating with ionic liquids.

Computational Reconstruction of Pacemaking and Intrinsic Electroresponsiveness in Cerebellar Golgi Cells

PubMed Central

Solinas, Sergio; Forti, Lia; Cesana, Elisabetta; Mapelli, Jonathan; De Schutter, Erik; D'Angelo, Egidio

2007-01-01

The Golgi cells have been recently shown to beat regularly in vitro (Forti et al., 2006. J. Physiol. 574, 711–729). Four main currents were shown to be involved, namely a persistent sodium current (I Na-p), an h current (I h), an SK-type calcium-dependent potassium current (I K-AHP), and a slow M-like potassium current (I K-slow). These ionic currents could take part, together with others, also to different aspects of neuronal excitability like responses to depolarizing and hyperpolarizing current injection. However, the ionic mechanisms and their interactions remained largely hypothetical. In this work, we have investigated the mechanisms of Golgi cell excitability by developing a computational model. The model predicts that pacemaking is sustained by subthreshold oscillations tightly coupled to spikes. I Na-p and I K-slow emerged as the critical determinants of oscillations. I h also played a role by setting the oscillatory mechanism into the appropriate membrane potential range. I K-AHP, though taking part to the oscillation, appeared primarily involved in regulating the ISI following spikes. The combination with other currents, in particular a resurgent sodium current (I Na-r) and an A-current (I K-A), allowed a precise regulation of response frequency and delay. These results provide a coherent reconstruction of the ionic mechanisms determining Golgi cell intrinsic electroresponsiveness and suggests important implications for cerebellar signal processing, which will be fully developed in a companion paper (Solinas et al., 2008. Front. Neurosci. 2:4). PMID:18946520

Physics of transduction in ionic liquid-swollen Nafion membranes

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2006-03-01

Ionic polymer transducers are a class of electroactive polymers that are able to generate large strains (1-5%) in response to low voltage inputs (1-5 V). Additionally, these materials generate electrical charge in response to mechanical strain and are therefore able to operate as soft, distributed sensors. Traditionally, ionic polymer transducers have been limited in their application by their hydration dependence. This work seeks to overcome this limitation by replacing the water with an ionic liquid. Ionic liquids are molten salts that exhibit very high thermal and electrochemical stability while also possessing high ionic conductivity. Results have shown that an ionic liquid-swollen ionic polymer transducer can operate for more than 250,000 cycles in air as compared to about 2,000 cycles for a water-swollen transducer. The current work examines the mechanisms of transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a model of the charge transport mechanism responsible for electromechanical coupling in these membranes.

Triboelectric energy harvesting with surface-charge-fixed polymer based on ionic liquid

PubMed Central

Sano, Chikako; Mitsuya, Hiroyuki; Ono, Shimpei; Miwa, Kazumoto; Toshiyoshi, Hiroshi; Fujita, Hiroyuki

2018-01-01

Abstract A novel triboelectric energy harvester has been developed using an ionic liquid polymer with cations fixed at the surface. In this report, the fabrication of the device and the characterization of its energy harvesting performance are detailed. An electrical double layer was induced in the ionic liquid polymer precursor to attract the cations to the surface where they are immobilized using a UV-based crosslinking reaction. The finalized polymer is capable of generating an electrical current when contacted by a metal electrode. Using this property, energy harvesting experiments were conducted by cyclically contacting a gold-surface electrode with the charge fixed surface of the polymer. Control experiments verified the effect of immobilizing the cations at the surface. By synthesizing a polymer with the optimal composition ratio of ionic liquid to macromonomer, an output of 77 nW/cm2 was obtained with a load resistance of 1 MΩ at 1 Hz. This tuneable power supply with a μA level current output may contribute to Internet of Things networks requiring numerous sensor nodes at remote places in the environment. PMID:29707070

ATP: a vasoactive signal in the pericyte-containing microvasculature of the rat retina

PubMed Central

Kawamura, Hajime; Sugiyama, Tetsuya; Wu, David M; Kobayashi, Masato; Yamanishi, Shigeki; Katsumura, Kozo; Puro, Donald G

2003-01-01

In this study we tested the hypothesis that extracellular ATP regulates the function of the pericyte-containing retinal microvessels. Pericytes, which are more numerous in the retina than in any other tissue, are abluminally located cells that may adjust capillary perfusion by contracting and relaxing. At present, knowledge of the vasoactive molecules that regulate pericyte function is limited. Here, we focused on the actions of extracellular ATP because this nucleotide is a putative glial-to-vascular signal, as well as being a substance released by activated platelets and injured cells. In microvessels freshly isolated from the adult rat retina, we monitored ionic currents via perforated-patch pipettes, measured intracellular calcium levels with the use of fura-2, and visualized microvascular contractions with the aid of time-lapse photography. We found that ATP induced depolarizing changes in the ionic currents, increased calcium levels and caused pericytes to contract. P2X7 receptors and UTP-activated receptors mediated these effects. Consistent with ATP serving as a vasoconstrictor for the pericyte-containing microvasculature of the retina, the microvascular lumen narrowed when an adjacent pericyte contracted. In addition, the sustained activation of P2X7 receptors inhibited cell-to-cell electrotonic transmission within the microvascular networks. Thus, ATP not only affects the contractility of individual pericytes, but also appears to regulate the spatial and temporal dynamics of the vasomotor response. PMID:12876212

Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

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

He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.

2011-08-01

The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationshipmore » between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.« less

Recent advances in the applications of ionic liquids in protein stability and activity: a review.

PubMed

Patel, Rajan; Kumari, Meena; Khan, Abbul Bashar

2014-04-01

Room temperatures ionic liquids are considered as miraculous solvents for biological system. Due to their inimitable properties and large variety of applications, they have been widely used in enzyme catalysis and protein stability and separation. The related information present in the current review is helpful to the researchers working in the field of biotechnology and biochemistry to design or choose an ionic liquid that can serve as a noble and selective solvent for any particular enzymatic reaction, protein preservation and other protein based applications. We have extensively analyzed the methods used for studying the protein-IL interaction which is useful in providing information about structural and conformational dynamics of protein. This can be helpful to develop and understanding about the effect of ionic liquids on stability and activity of proteins. In addition, the affect of physico-chemical properties of ionic liquids, viz. hydrogen bond capacity and hydrophobicity on protein stability are discussed.

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids.

PubMed

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situ scanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situ STM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situ microscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).

Role of Oxygen in Ionic Liquid Gating on Two-Dimensional Cr2Ge2Te6: A Non-oxide Material.

PubMed

Chen, Yangyang; Xing, Wenyu; Wang, Xirui; Shen, Bowen; Yuan, Wei; Su, Tang; Ma, Yang; Yao, Yunyan; Zhong, Jiangnan; Yun, Yu; Xie, X C; Jia, Shuang; Han, Wei

2018-01-10

Ionic liquid gating can markedly modulate a material's carrier density so as to induce metallization, superconductivity, and quantum phase transitions. One of the main issues is whether the mechanism of ionic liquid gating is an electrostatic field effect or an electrochemical effect, especially for oxide materials. Recent observation of the suppression of the ionic liquid gate-induced metallization in the presence of oxygen for oxide materials suggests the electrochemical effect. However, in more general scenarios, the role of oxygen in the ionic liquid gating effect is still unclear. Here, we perform ionic liquid gating experiments on a non-oxide material: two-dimensional ferromagnetic Cr 2 Ge 2 Te 6 . Our results demonstrate that despite the large increase of the gate leakage current in the presence of oxygen, the oxygen does not affect the ionic liquid gating effect on  the channel resistance of Cr 2 Ge 2 Te 6 devices (<5% difference), which suggests the electrostatic field effect as the mechanism on non-oxide materials. Moreover, our results show that ionic liquid gating is more effective on the modulation of the channel resistances compared to the back gating across the 300 nm thick SiO 2 .

Sequencing proteins with transverse ionic transport in nanochannels.

PubMed

Boynton, Paul; Di Ventra, Massimiliano

2016-05-03

De novo protein sequencing is essential for understanding cellular processes that govern the function of living organisms and all sequence modifications that occur after a protein has been constructed from its corresponding DNA code. By obtaining the order of the amino acids that compose a given protein one can then determine both its secondary and tertiary structures through structure prediction, which is used to create models for protein aggregation diseases such as Alzheimer's Disease. Here, we propose a new technique for de novo protein sequencing that involves translocating a polypeptide through a synthetic nanochannel and measuring the ionic current of each amino acid through an intersecting perpendicular nanochannel. We find that the distribution of ionic currents for each of the 20 proteinogenic amino acids encoded by eukaryotic genes is statistically distinct, showing this technique's potential for de novo protein sequencing.

Efficient platinum-free counter electrodes for dye-sensitized solar cell applications.

PubMed

Ahmad, Shahzada; Yum, Jun-Ho; Butt, Hans-Jürgen; Nazeeruddin, Mohammad K; Grätzel, Michael

2010-09-10

Nanoporous layers of poly(3,4-propylenedioxythiophene) (PProDOT) were fabricated by electrical-field-assisted growth using hydrophobic ionic liquids as the growing medium. A series of PProDoT layers was prepared with three different ionic liquids to control the microstructure and electrochemical properties of the resulting dye-sensitized solar cells, which were highly efficient and showed a power conversion efficiency of >9% under different sunlight intensities. The current-voltage characteristics of the counter electrodes varied depending on the ionic liquids used in the synthesis of PProDOT. The most hydrophobic ionic liquids exhibited high catalytic properties, thus resulting in high power conversion efficiency and allowing the fabrication of platinum-free, stable, flexible, and cost-effective dye-sensitized solar cells.

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Molecular modeling of field-driven ion emission from ionic liquids

NASA Astrophysics Data System (ADS)

Zhang, Fei; He, Yadong; Qiao, Rui

2017-11-01

Traditionally, operating electrosprays in the purely ionic mode is challenging, but recent experiments confirmed that such operation can be achieved using room-temperature ionic liquids as working electrolytes. Such electrosprays have shown promise in applications including chemical analysis, nanomanufacturing, and space propulsion. The mechanistic and quantitative understanding of such electrosprays at the molecular level, however, remain limited at present. In this work, we simulated ion emission from EMIM-PF6 ionic liquid films using the molecular dynamics method. We show that, when the surface electric field is smaller than 1.5V/nm, the ion emission current predicted using coarse-grained ionic liquid model observes the classical scaling law by J. V. Iribarne and B. A. Thomson, i.e., ln(Je/ σ) En1/2. These simulations, however, cannot capture the co-emission of cations and anions from ionic liquid surface observed in some experiments. Such co-emission was successfully captured when united-atom models were adopted for the ionic liquids. By examining the co-emission events with picosecond, sub-angstrom resolution, we clarified the origins of the co-emission phenomenon and delineate the molecular events leading to ion emission.

Individual and Co Transport Study of Titanium Dioxide NPs and Zinc Oxide NPs in Porous Media

PubMed Central

Kumari, Jyoti; Mathur, Ankita; Rajeshwari, A.; Venkatesan, Arthi; S, Satyavati; Pulimi, Mrudula; Chandrasekaran, Natarajan; Nagarajan, R.; Mukherjee, Amitava

2015-01-01

The impact of pH and ionic strength on the mobility (individual and co-transport) and deposition kinetics of TiO2 and ZnO NPs in porous media was systematically investigated in this study. Packed column experiments were performed over a series of environmentally relevant ionic strengths with both NaCl (0.1−10 mM) and CaCl2 (0.01–0.1mM) solutions and at pH 5, 7, and 9. The transport of TiO2 NPs at pH 5 was not significantly affected by ZnO NPs in solution. At pH 7, a decrease in TiO2 NP transport was noted with co-existence of ZnO NPs, while at pH 9 an increase in the transport was observed. At pH 5 and 7, the transport of ZnO NPs was decreased when TiO2 NPs was present in the solution, and at pH 9, an increase was noted. The breakthrough curves (BTC) were noted to be sensitive to the solution chemistries; the decrease in the breakthrough plateau with increasing ionic strength was observed under all examined pH (5, 7, and 9). The retention profiles were the inverse of the plateaus of BTCs, as expected from mass balance considerations. Overall, the results from this study suggest that solution chemistries (ionic strength and pH) are likely the key factors that govern the individual and co-transport behavior of TiO2 and ZnO NPs in sand. PMID:26252479

Rapid structural analysis of nanomaterials in aqueous solutions

NASA Astrophysics Data System (ADS)

Ryuzaki, Sou; Tsutsui, Makusu; He, Yuhui; Yokota, Kazumichi; Arima, Akihide; Morikawa, Takanori; Taniguchi, Masateru; Kawai, Tomoji

2017-04-01

Rapid structural analysis of nanoscale matter in a liquid environment represents innovative technologies that reveal the identities and functions of biologically important molecules. However, there is currently no method with high spatio-temporal resolution that can scan individual particles in solutions to gain structural information. Here we report the development of a nanopore platform realizing quantitative structural analysis for suspended nanomaterials in solutions with a high z-axis and xy-plane spatial resolution of 35.8 ± 1.1 and 12 nm, respectively. We used a low thickness-to-diameter aspect ratio pore architecture for achieving cross sectional areas of analyte (i.e. tomograms). Combining this with multiphysics simulation methods to translate ionic current data into tomograms, we demonstrated rapid structural analysis of single polystyrene (Pst) beads and single dumbbell-like Pst beads in aqueous solutions.

Ionic Components of Electric Current at Rat Corneal Wounds

PubMed Central

Cao, Lin; Mannis, Mark J.; Schwab, Ivan R.; Zhao, Min

2011-01-01

Background Endogenous electric fields and currents occur naturally at wounds and are a strong signal guiding cell migration into the wound to promote healing. Many cells involved in wound healing respond to small physiological electric fields in vitro. It has long been assumed that wound electric fields are produced by passive ion leakage from damaged tissue. Could these fields be actively maintained and regulated as an active wound response? What are the molecular, ionic and cellular mechanisms underlying the wound electric currents? Methodology/Principal Findings Using rat cornea wounds as a model, we measured the dynamic timecourses of individual ion fluxes with ion-selective probes. We also examined chloride channel expression before and after wounding. After wounding, Ca2+ efflux increased steadily whereas K+ showed an initial large efflux which rapidly decreased. Surprisingly, Na+ flux at wounds was inward. A most significant observation was a persistent large influx of Cl−, which had a time course similar to the net wound electric currents we have measured previously. Fixation of the tissues abolished ion fluxes. Pharmacological agents which stimulate ion transport significantly increased flux of Cl−, Na+ and K+. Injury to the cornea caused significant changes in distribution and expression of Cl− channel CLC2. Conclusions/Significance These data suggest that the outward electric currents occurring naturally at corneal wounds are carried mainly by a large influx of chloride ions, and in part by effluxes of calcium and potassium ions. Ca2+ and Cl− fluxes appear to be mainly actively regulated, while K+ flux appears to be largely due to leakage. The dynamic changes of electric currents and specific ion fluxes after wounding suggest that electrical signaling is an active response to injury and offers potential novel approaches to modulate wound healing, for example eye-drops targeting ion transport to aid in the challenging management of non-healing corneal ulcers. PMID:21364900

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Modeling Unipolar and Bipolar Stimulation of Cardiac Tissue

NASA Astrophysics Data System (ADS)

Galappaththige, Suran Kokila

Out of all non-communicable diseases, heart diseases have become the leading cause of death and disease burden worldwide. Heart diseases describe a variety of circumstances that affect your heart. One common condition is the heart rhythm problem often called an arrhythmia. The rhythmic beating of the human heart can be altered due to various reasons. This inconsistency in beating can lead to a lethal form of arrhythmia that we call ventricular fibrillation. We treat fibrillation by applying an electrical shock to the heart using a unipolar electrode or bipolar electrodes. To build better pace makers and defibrillators, we must understand how the heart responds to an electrical shock. One way to study cardiac arrhythmias is using a mathematical model. The computational biology of the heart is one of the most important recent applications of mathematical modeling in biology. By using mathematical models, we can understand the mechanisms responsible of the heart's electrical behavior. We investigate if the time-independent, inwardly rectifying potassium current through the cell membrane inhibits the hyperpolarization after a stimulus electrical pulse is applied to the resting heart tissue. The inhibition of hyperpolarization is due to long duration stimulus pulses, but not short duration pulses. We also investigate the minimum conditions required for the dip in strength-interval curves using a simple but not so simple parsimonious ionic current model coupled with the bidomain model. Unipolar anodal stimulations still results in the dip in the strength-interval curves and this explains the minimum conditions for this phenomenon to occur. Bipolar stimulation of cardiac tissue using the parsimonious ionic current model revels that the strength-interval curves are sensitive to the separation between electrodes and the electrode orientation relative to the fiber direction. One of the ionic currents in the parsimonious ionic current model mimics the time-independent inwardly rectifying potassium current and this study examines the importance of this current in mathematical models that describe cardiac electrical behavior.

High performance photolithographically-patterned polymer thin-film transistors gated with an ionic liquid/poly(ionic liquid) blend ion gel

NASA Astrophysics Data System (ADS)

Thiburce, Q.; Porcarelli, L.; Mecerreyes, D.; Campbell, A. J.

2017-06-01

We demonstrate the fabrication of polymer thin-film transistors gated with an ion gel electrolyte made of the blend of an ionic liquid and a polymerised ionic liquid. The ion gel exhibits a high stability and ionic conductivity, combined with facile processing by simple drop-casting from solution. In order to avoid parasitic effects such as high hysteresis, high off-currents, and slow switching, a fluorinated photoresist is employed in order to enable high-resolution orthogonal patterning of the polymer semiconductor over an area that precisely defines the transistor channel. The resulting devices exhibit excellent characteristics, with an on/off ratio of 106, low hysteresis, and a very large transconductance of 3 mS. We show that this high transconductance value is mostly the result of ions penetrating the polymer film and doping the entire volume of the semiconductor, yielding an effective capacitance per unit area of about 200 μF cm-2, one order of magnitude higher than the double layer capacitance of the ion gel. This results in channel currents larger than 1 mA at an applied gate bias of only -1 V. We also investigate the dynamic performance of the devices and obtain a switching time of 20 ms, which is mostly limited by the overlap capacitance between the ion gel and the source and drain contacts.

Symmetric supercapacitor: Sulphurized graphene and ionic liquid.

PubMed

Shaikh, Jasmin S; Shaikh, Navajsharif S; Kharade, Rohini; Beknalkar, Sonali A; Patil, Jyoti V; Suryawanshi, Mahesh P; Kanjanaboos, Pongsakorn; Hong, Chang Kook; Kim, Jin Hyeok; Patil, Pramod S

2018-10-01

Symmetric supercapacitor is advanced over simple supercapacitor device due to their stability over a large potential window and high energy density. Graphene is a desired candidate for supercapacitor application since it has a high surface area, good electronic conductivity and high electro chemical stability. There is a pragmatic use of ionic liquid electrolyte for supercapacitor due to its stability over a large potential window, good ionic conductivity and eco-friendly nature. For high performance supercapacitor, the interaction between ionic liquid electrolyte and graphene are crucial for better charge transportation. In respect of this, a three-dimensional (3D) nanoporous honeycomb shaped sulfur embedded graphene (S-graphene) has been synthesized by simple chemical method. Here, the fabrication of high performance symmetric supercapacitor is done by using S-graphene as an electrode and [BMIM-PF 6 ] as an electrolyte. The particular architecture of S-graphene benefited to reduce the ion diffusion resistance, providing the large surface area for charge transportation and efficient charge storage. The S-graphene and ionic liquid-based symmetric supercapacitor device showed the large potential window of 3.2 V with high energy density 124 Wh kg -1 at 0.2 A g -1 constant applied current density. Furthermore, this device shows good cycling performance (stability) with a capacitive retention of 95% over 20,000 cycles at a higher current density of 2 A g -1 . Copyright © 2018 Elsevier Inc. All rights reserved.

Surface effects on ionic Coulomb blockade in nanometer-size pores

NASA Astrophysics Data System (ADS)

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V.; Di Ventra, Massimiliano

2018-01-01

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying ‘crystal-like’ structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Surface effects on ionic Coulomb blockade in nanometer-size pores.

PubMed

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V; Ventra, Massimiliano Di

2018-01-12

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying 'crystal-like' structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Global transcriptome response to ionic liquid by a tropical rain forest soil bacterium, Enterobacter lignolyticus.

PubMed

Khudyakov, Jane I; D'haeseleer, Patrik; Borglin, Sharon E; Deangelis, Kristen M; Woo, Hannah; Lindquist, Erika A; Hazen, Terry C; Simmons, Blake A; Thelen, Michael P

2012-08-07

To process plant-based renewable biofuels, pretreatment of plant feedstock with ionic liquids has significant advantages over current methods for deconstruction of lignocellulosic feedstocks. However, ionic liquids are often toxic to the microorganisms used subsequently for biomass saccharification and fermentation. We previously isolated Enterobacter lignolyticus strain SCF1, a lignocellulolytic bacterium from tropical rain forest soil, and report here that it can grow in the presence of 0.5 M 1-ethyl-3-methylimidazolium chloride, a commonly used ionic liquid. We investigated molecular mechanisms of SCF1 ionic liquid tolerance using a combination of phenotypic growth assays, phospholipid fatty acid analysis, and RNA sequencing technologies. Potential modes of resistance to 1-ethyl-3-methylimidazolium chloride include an increase in cyclopropane fatty acids in the cell membrane, scavenging of compatible solutes, up-regulation of osmoprotectant transporters and drug efflux pumps, and down-regulation of membrane porins. These findings represent an important first step in understanding mechanisms of ionic liquid resistance in bacteria and provide a basis for engineering microbial tolerance.

Highly Transparent, Stretchable, and Self-Healing Ionic-Skin Triboelectric Nanogenerators for Energy Harvesting and Touch Applications.

PubMed

Parida, Kaushik; Kumar, Vipin; Jiangxin, Wang; Bhavanasi, Venkateswarlu; Bendi, Ramaraju; Lee, Pooi See

2017-10-01

Recently developed triboelectric nanogenerators (TENGs) act as a promising power source for self-powered electronic devices. However, the majority of TENGs are fabricated using metallic electrodes and cannot achieve high stretchability and transparency, simultaneously. Here, slime-based ionic conductors are used as transparent current-collecting layers of TENG, thus significantly enhancing their energy generation, stretchability, transparency, and instilling self-healing characteristics. This is the first demonstration of using an ionic conductor as the current collector in a mechanical energy harvester. The resulting ionic-skin TENG (IS-TENG) has a transparency of 92% transmittance, and its energy-harvesting performance is 12 times higher than that of the silver-based electronic current collectors. In addition, they are capable of enduring a uniaxial strain up to 700%, giving the highest performance compared to all other transparent and stretchable mechanical-energy harvesters. Additionally, this is the first demonstration of an autonomously self-healing TENG that can recover its performance even after 300 times of complete bifurcation. The IS-TENG represents the first prototype of a highly deformable and transparent power source that is able to autonomously self-heal quickly and repeatedly at room temperature, and thus can be used as a power supply for digital watches, touch sensors, artificial intelligence, and biointegrated electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of concentration polarization on DNA translocation through a nanopore.

PubMed

Zhai, Shengjie; Zhao, Hui

2016-05-01

Concentration polarization can be induced by the unique ion-perm selectivity of small nanopores, leading to a salt concentration gradient across nanopores. This concentration gradient can create diffusio-osmosis and induce an electric field, affecting ionic currents on DNA that translocates through a nanopore. Here this influence is theoretically investigated by solving the continuum Poisson-Nernst-Planck model for different salt concentrations, DNA surface charge densities, and pore properties. By implementing the perturbation method, we can explicitly compute the contribution of concentration polarization to the ionic current. The induced electric field by concentration polarization is opposite to the imposed electric field and decreases the migration current, and the induced diffusio-osmosis can decrease the convection current as well. Our studies suggest that the importance of the concentration polarization can be determined by the parameter λ/G where λ is the double-layer thickness and G is the gap size. When λ/G is larger than a critical value, the influence of concentration polarization becomes more prominent. This conclusion is supported by the studies on the dependence of the ionic current on salt concentration and pore properties, showing that the difference between two models with and without accounting for concentration polarization is larger for low salts and small pores, which correspond to larger λ/G.

Dissection of the Voltage Losses of an Acidic Quinone Redox Flow Battery

DOE PAGES

Chen, Qing; Gerhardt, Michael R.; Aziz, Michael J.

2017-03-28

We measure the polarization characteristics of a quinone-bromide redox flow battery with interdigitated flow fields, using electrochemical impedance spectroscopy and voltammetry of a full cell and of a half cell against a reference electrode. We find linear polarization behavior at 50% state of charge all the way to the short-circuit current density of 2.5 A/cm 2. We uniquely identify the polarization area-specific resistance (ASR) of each electrode, the membrane ASR to ionic current, and the electronic contact ASR. We use voltage probes to deduce the electronic current density through each sheet of carbon paper in the quinone-bearing electrode. By alsomore » interpreting the results using the Newman 1-D porous electrode model, we deduce the volumetric exchange current density of the porous electrode. We uniquely evaluate the power dissipation and identify a correspondence to the contributions to the electrode ASR from the faradaic, electronic, and ionic transport processes. We find that, within the electrode, more power is dissipated in the faradaic process than in the electronic and ionic conduction processes combined, despite the observed linear polarization behavior. We examine the sensitivity of the ASR to the values of the model parameters. The greatest performance improvement is anticipated from increasing the volumetric exchange current density.« less

Understanding electrical conduction in lithium ion batteries through multi-scale modeling

NASA Astrophysics Data System (ADS)

Pan, Jie

Silicon (Si) has been considered as a promising negative electrode material for lithium ion batteries (LIBs) because of its high theoretical capacity, low discharge voltage, and low cost. However, the utilization of Si electrode has been hampered by problems such as slow ionic transport, large stress/strain generation, and unstable solid electrolyte interphase (SEI). These problems severely influence the performance and cycle life of Si electrodes. In general, ionic conduction determines the rate performance of the electrode, while electron leakage through the SEI causes electrolyte decomposition and, thus, causes capacity loss. The goal of this thesis research is to design Si electrodes with high current efficiency and durability through a fundamental understanding of the ionic and electronic conduction in Si and its SEI. Multi-scale physical and chemical processes occur in the electrode during charging and discharging. This thesis, thus, focuses on multi-scale modeling, including developing new methods, to help understand these coupled physical and chemical processes. For example, we developed a new method based on ab initio molecular dynamics to study the effects of stress/strain on Li ion transport in amorphous lithiated Si electrodes. This method not only quantitatively shows the effect of stress on ionic transport in amorphous materials, but also uncovers the underlying atomistic mechanisms. However, the origin of ionic conduction in the inorganic components in SEI is different from that in the amorphous Si electrode. To tackle this problem, we developed a model by separating the problem into two scales: 1) atomistic scale: defect physics and transport in individual SEI components with consideration of the environment, e.g., LiF in equilibrium with Si electrode; 2) mesoscopic scale: defect distribution near the heterogeneous interface based on a space charge model. In addition, to help design better artificial SEI, we further demonstrated a theoretical design of multicomponent SEIs by utilizing the synergetic effect found in the natural SEI. We show that the electrical conduction can be optimized by varying the grain size and volume fraction of two phases in the artificial multicomponent SEI.

Characterization of ionic currents of cells of the subfornical organ that project to the supraoptic nuclei

NASA Technical Reports Server (NTRS)

Johnson, R. F.; Beltz, T. G.; Jurzak, M.; Wachtel, R. E.; Johnson, A. K.

1999-01-01

The subfornical organ (SFO) is a forebrain structure that converts peripheral blood-borne signals reflecting the hydrational state of the body to neural signals and then through efferent fibers conveys this information to several central nervous system structures. One of the forebrain areas receiving input from the SFO is the supraoptic nucleus (SON), a source of vasopressin synthesis and control of release from the posterior pituitary. Little is known of the transduction and transmission processes by which this conversion of systemic information to brain input occurs. As a step in elucidating these mechanisms, the present study characterized the ionic currents of dissociated cells of the SFO that were identified as neurons that send efferents to the SON. A retrograde tracer was injected into the SON area in eleven-day-old rats. After three days for retrograde transport of the label, the SFOs of these animals were dissociated and plated for tissue culture. The retrograde tracer was used to identify the soma of SFO cells projecting to the SON so that voltage-dependent ionic currents using whole-cell voltage clamp methods could be studied. The three types of currents in labeled SFO neurons were characterized as a 1) rapid, transient inward current that can be blocked by tetrodotoxin (TTX) characteristic of a sodium current; 2) slow-onset sustained outward current that can be blocked by tetraethylammonium (TEA) characteristic of a delayed rectifier potassium current; and 3) remaining outward current that has a rapid-onset and transient characteristic of a potassium A-type current. Copyright 1999 Elsevier Science B.V.

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

NASA Technical Reports Server (NTRS)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

Liquid methanol under a static electric field

NASA Astrophysics Data System (ADS)

Cassone, Giuseppe; Giaquinta, Paolo V.; Saija, Franz; Saitta, A. Marco

2015-02-01

We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm-1) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

Memory in a fractional-order cardiomyocyte model alters properties of alternans and spontaneous activity

NASA Astrophysics Data System (ADS)

Comlekoglu, T.; Weinberg, S. H.

2017-09-01

Cardiac memory is the dependence of electrical activity on the prior history of one or more system state variables, including transmembrane potential (Vm), ionic current gating, and ion concentrations. While prior work has represented memory either phenomenologically or with biophysical detail, in this study, we consider an intermediate approach of a minimal three-variable cardiomyocyte model, modified with fractional-order dynamics, i.e., a differential equation of order between 0 and 1, to account for history-dependence. Memory is represented via both capacitive memory, due to fractional-order Vm dynamics, that arises due to non-ideal behavior of membrane capacitance; and ionic current gating memory, due to fractional-order gating variable dynamics, that arises due to gating history-dependence. We perform simulations for varying Vm and gating variable fractional-orders and pacing cycle length and measure action potential duration (APD) and incidence of alternans, loss of capture, and spontaneous activity. In the absence of ionic current gating memory, we find that capacitive memory, i.e., decreased Vm fractional-order, typically shortens APD, suppresses alternans, and decreases the minimum cycle length (MCL) for loss of capture. However, in the presence of ionic current gating memory, capacitive memory can prolong APD, promote alternans, and increase MCL. Further, we find that reduced Vm fractional order (typically less than 0.75) can drive phase 4 depolarizations that promote spontaneous activity. Collectively, our results demonstrate that memory reproduced by a fractional-order model can play a role in alternans formation and pacemaking, and in general, can greatly increase the range of electrophysiological characteristics exhibited by a minimal model.

Part-II: Exchange current density and ionic diffusivity studies on the ordered and disordered spinel LiNi0.5Mn1.5O4 cathode

NASA Astrophysics Data System (ADS)

Amin, Ruhul; Belharouak, Ilias

2017-04-01

Additive-free pellets of Li1-xNi0.5Mn1.5O4 have been prepared for the purpose of performing ionic diffusivity and exchange current density studies. Here we report on the characterization of interfacial charge transfer kinetics and ionic diffusivity of ordered (P4332) and disordered (Fd 3 bar m) Li1-xNi0.5Mn1.5O4 as a function of lithium content at ambient temperature. The exchange current density at the electrode/electrolyte interface is found to be continuously increased with increasing the degree of delithiation for ordered phase (∼0.21-6.5 mA/cm2) at (x = 0.01-0.60), in contrast the disordered phase exhibits gradually decrease of exchange current density in the initial delithiation at the 4 V plateau regime (x = 0.01-0.04) and again monotonously increases (0.65-6.8 mA/cm2) with further delithiation at (x = 0.04-0.60). The ionic diffusivity of ordered and disordered phase is found to be ∼5 × 10-10cm2s-1 and ∼10-9cm2s-1, respectively, and does not vary much with the degree of delithiation. From the obtained results it appears that the chemical diffusivity during electrochemical use is limited by lithium transport, but is fast enough over the entire state-of-charge range to allow charge/discharge of micron-scale particles at practical C-rates.

Robust High-performance Dye-sensitized Solar Cells Based on Ionic Liquid-sulfolane Composite Electrolytes.

PubMed

Lau, Genevieve P S; Décoppet, Jean-David; Moehl, Thomas; Zakeeruddin, Shaik M; Grätzel, Michael; Dyson, Paul J

2015-12-16

Novel ionic liquid-sulfolane composite electrolytes based on the 1,2,3-triazolium family of ionic liquids were developed for dye-sensitized solar cells. The best performing device exhibited a short-circuit current density of 13.4 mA cm(-2), an open-circuit voltage of 713 mV and a fill factor of 0.65, corresponding to an overall power conversion efficiency (PCE) of 6.3%. In addition, these devices are highly stable, retaining more than 95% of the initial device PCE after 1000 hours of light- and heat-stress. These composite electrolytes show great promise for industrial application as they allow for a 14.5% improvement in PCE, compared to the solvent-free eutectic ionic liquid electrolyte system, without compromising device stability.

Dynamic, nonlinear feedback regulation of slow pacemaking by A-type potassium current in ventral tegmental area neurons.

PubMed

Khaliq, Zayd M; Bean, Bruce P

2008-10-22

We analyzed ionic currents that regulate pacemaking in dopaminergic neurons of the mouse ventral tegmental area by comparing voltage trajectories during spontaneous firing with ramp-evoked currents in voltage clamp. Most recordings were made in brain slice, with key experiments repeated using acutely dissociated neurons, which gave identical results. During spontaneous firing, net ionic current flowing between spikes was calculated from the time derivative of voltage multiplied by cell capacitance, signal-averaged over many firing cycles to enhance resolution. Net inward interspike current had a distinctive nonmonotonic shape, reaching a minimum (generally <1 pA) between -60 and -55 mV. Under voltage clamp, ramps over subthreshold voltages elicited a time- and voltage-dependent outward current that peaked near -55 mV. This current was undetectable with 5 mV/s ramps and increased steeply with depolarization rate over the range (10-50 mV/s) typical of natural pacemaking. Ramp-evoked subthreshold current was resistant to alpha-dendrotoxin, paxilline, apamin, and tetraethylammonium but sensitive to 4-aminopyridine and 0.5 mM Ba2+, consistent with A-type potassium current (I(A)). Same-cell comparison of currents elicited by various ramp speeds with natural spontaneous depolarization showed how the steep dependence of I(A) on depolarization rate results in small net inward currents during pacemaking. These results reveal a mechanism in which subthreshold I(A) is near zero at steady state, but is engaged at depolarization rates >10 mV/s to act as a powerful, supralinear feedback element. This feedback mechanism explains how net ionic current can be constrained to <1-2 pA but reliably inward, thus enabling slow, regular firing.

Contributions of the Model of Modelling Diagram to the Learning of Ionic Bonding: Analysis of a Case Study

ERIC Educational Resources Information Center

Mendonca, Paula Cristina Cardoso; Justi, Rosaria

2011-01-01

Current proposals for science education recognise the importance of students' involvement in activities aimed at favouring the understanding of science as a human, dynamic and non-linear construct. Modelling-based teaching is one of the alternatives through which to address such issues. Modelling-based teaching activities for ionic bonding were…

Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids.

PubMed

Poole, Colin F

2004-05-28

Room temperature ionic liquids are novel solvents with favorable environmental and technical features. Synthetic routes to over 200 room temperature ionic liquids are known but for most ionic liquids physicochemical data are generally lacking or incomplete. Chromatographic and spectroscopic methods afford suitable tools for the study of solvation properties under conditions that approximate infinite dilution. Gas-liquid chromatography is suitable for the determination of gas-liquid partition coefficients and activity coefficients as well as thermodynamic constants derived from either of these parameters and their variation with temperature. The solvation parameter model can be used to define the contribution from individual intermolecular interactions to the gas-liquid partition coefficient. Application of chemometric procedures to a large database of system constants for ionic liquids indicates their unique solvent properties: low cohesion for ionic liquids with weakly associated ions compared with non-ionic liquids of similar polarity; greater hydrogen-bond basicity than typical polar non-ionic solvents; and a range of dipolarity/polarizability that encompasses the same range as occupied by the most polar non-ionic liquids. These properties can be crudely related to ion structures but further work is required to develop a comprehensive approach for the design of ionic liquids for specific applications. Data for liquid-liquid partition coefficients is scarce by comparison with gas-liquid partition coefficients. Preliminary studies indicate the possibility of using the solvation parameter model for interpretation of liquid-liquid partition coefficients determined by shake-flask procedures as well as the feasibility of using liquid-liquid chromatography for the convenient and rapid determination of liquid-liquid partition coefficients. Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ionic liquids provide insights into solvent intermolecular interactions although interpretation of the different and generally uncorrelated "polarity" scales is sometimes ambiguous. All evidence points to the ionic liquids as a unique class of polar solvents suitable for technical development. In terms of designer solvents, however, further work is needed to fill the gaps in our knowledge of the relationship between ion structures and physicochemical properties.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Electronic functions of solid-to-liquid interfaces of organic semiconductor crystals and ionic liquid

NASA Astrophysics Data System (ADS)

Takeya, J.

2008-10-01

The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

PubMed

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

Characterization of individual polynucleotide molecules using a membrane channel

NASA Technical Reports Server (NTRS)

Kasianowicz, J. J.; Brandin, E.; Branton, D.; Deamer, D. W.

1996-01-01

We show that an electric field can drive single-stranded RNA and DNA molecules through a 2.6-nm diameter ion channel in a lipid bilayer membrane. Because the channel diameter can accommodate only a single strand of RNA or DNA, each polymer traverses the membrane as an extended chain that partially blocks the channel. The passage of each molecule is detected as a transient decrease of ionic current whose duration is proportional to polymer length. Channel blockades can therefore be used to measure polynucleotide length. With further improvements, the method could in principle provide direct, high-speed detection of the sequence of bases in single molecules of DNA or RNA.

Research Update: Fast and tunable nanoionics in vertically aligned nanostructured films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; MacManus-Driscoll, Judith L.

2017-04-01

This review provides the design principles to develop new nanoionic applications using vertically aligned nanostructured (VAN) thin films, incorporating two phases which self-assemble in one film. Tunable nanoionics has attracted great attention for energy and device applications, such as ion batteries, solid oxide fuel cells, catalysts, memories, and neuromorphic devices. Among many proposed device architectures, VAN films have strong potential for nanoionic applications since they show enhanced ionic conductivity and tunability. Here, we will review the recent progress on state-of-the-art nanoionic applications, which have been realized by using VAN films. In many VAN systems made by the inclusion of an oxygen ionic insulator, it is found that ions flow through the vertical heterointerfaces. The observation is consistent with structural incompatibility at the vertical heteroepitaxial interfaces resulting in oxygen deficiency in one of the phases and hence to oxygen ion conducting pathways. In other VAN systems where one of the phases is an ionic conductor, ions flow much faster within the ionic conducting phase than within the corresponding plain film. The improved ionic conduction coincides with much improved crystallinity in the ionically conducting nanocolumnar phase, induced by use of the VAN structure. Furthermore, for both cases Joule heating effects induced by localized ionic current flow also play a role for enhanced ionic conductivity. Nanocolumn stoichiometry and strain are other important parameters for tuning ionic conductivity in VAN films. Finally, double-layered VAN film architectures are discussed from the perspective of stabilizing VAN structures which would be less stable and hence less perfect when grown on standard substrates.

Effects of wastewater sludge and its detergents on the stability of rotavirus

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

Ward, R.L.; Ashley, C.S.

1980-06-01

Wastewater sludge reduced the heat required to inactivate rotavirus SA-11, and ionic detergents were identified as the sludge components responsible for this effect. A similar result was found previously with reovirus. The quantitative effects of individual ionic detergents on rotavirus and reovirus were very different, and rotavirus was found to be extremely sensitive to several of these detergents. However, neither virus was destabilized by nonionic detergents. On the contrary, rotavirus was stabilized by a nonionic detergent against the potent destabilizing effects of the ionic detergent sodium dodecyl sulfate. The destabilizing effects of both cationic and anionic detergents on rotavirus weremore » greatly altered by changes in the pH of the medium.« less

Expression of a Deschampsia antarctica Desv. Polypeptide with Lipase Activity in a Pichia pastoris Vector

PubMed Central

Rabert, Claudia; Gutiérrez-Moraga, Ana; Navarrete-Gallegos, Alejandro; Navarrete-Campos, Darío; Bravo, León A.; Gidekel, Manuel

2014-01-01

The current study isolated and characterized the Lip3F9 polypeptide sequence of Deschampsia antarctica Desv. (GeneBank Accession Number JX846628), which was found to be comprised of 291 base pairs and was, moreover, expressed in Pichia pastoris X-33 cells. The enzyme was secreted after 24 h of P. pastoris culture incubation and through induction with methanol. The expressed protein showed maximum lipase activity (35 U/L) with an optimal temperature of 37 °C. The lipase-expressed enzyme lost 50% of its specific activity at 25 °C, a behavior characteristic of a psychrotolerant enzyme. Recombinant enzyme activity was measured in the presence of ionic and non-ionic detergents, and a decrease in enzyme activity was detected for all concentrations of ionic and non-ionic detergents assessed. PMID:24514564

Comparative Experimental Study on Ionic Polymer Mental Composite based on Nafion and Aquivion Membrane as Actuators

NASA Astrophysics Data System (ADS)

Luo, B.; Chen, Z.

2017-11-01

Most ionic polymer mental composites employ Nafion as the polymer matrix, Aquivion can also manufactured as ionic polymer mental composite while research was little. This paper researched on two kinds of ionic polymer mental composite based on Aquivion and Nafion matrix with palladium electrode called Aquivion-IPMC and Nafion-IPMC. The samples were fabricated by the same preparation process. The current and deformation responses of the samples were measured at voltage to characterize the mechano-electrical properties. The experimental observations revealed that shorter flexible side chains in Aquivion-IPMC provide a larger force than Nafion-IPMC, while the displacement properties were similar in two different samples. The results also showed that Aquivion membrane can also replace Nafion to reproduce IPMC application in soft robots, MEMS, and so on.

How the early voltage clamp studies of José del Castillo inform "modern" neuroscience.

PubMed

Zottoli, Steven J

2012-10-01

The description of ionic currents that flow across the membrane of the squid giant axon during an action potential sparked an interest in determining whether there were similar currents in vertebrates. The preparation of choice was the node of Ranvier in single myelinated fibers in frog. José del Castillo spent 3 years on the United States mainland from 1956 to 1959. During that time, he collaborated with Jerome Y. Lettvin and John W. Moore. I discuss how these individuals met one another and some of their scientific discoveries using the voltage clamp to study squid giant axons and frog nodes. Much of this work was conducted at the Marine Biological Laboratory in Woods Hole, MA, and I attempt to convey a sense of the unique scientific "melting pot" that existed at the Marine Biological Laboratory and the broader effect that del Castillo had on "modern" neuroscience.

Real space mapping of oxygen vacancy diffusion and electrochemical transformations by hysteretic current reversal curve measurements

DOEpatents

Kalinin, Sergei V.; Balke, Nina; Borisevich, Albina Y.; Jesse, Stephen; Maksymovych, Petro; Kim, Yunseok; Strelcov, Evgheni

2014-06-10

An excitation voltage biases an ionic conducting material sample over a nanoscale grid. The bias sweeps a modulated voltage with increasing maximal amplitudes. A current response is measured at grid locations. Current response reversal curves are mapped over maximal amplitudes of the bias cycles. Reversal curves are averaged over the grid for each bias cycle and mapped over maximal bias amplitudes for each bias cycle. Average reversal curve areas are mapped over maximal amplitudes of the bias cycles. Thresholds are determined for onset and ending of electrochemical activity. A predetermined number of bias sweeps may vary in frequency where each sweep has a constant number of cycles and reversal response curves may indicate ionic diffusion kinetics.

Series resistance compensation for whole-cell patch-clamp studies using a membrane state estimator

PubMed Central

Sherman, AJ; Shrier, A; Cooper, E

1999-01-01

Whole-cell patch-clamp techniques are widely used to measure membrane currents from isolated cells. While suitable for a broad range of ionic currents, the series resistance (R(s)) of the recording pipette limits the bandwidth of the whole-cell configuration, making it difficult to measure rapid ionic currents. To increase bandwidth, it is necessary to compensate for R(s). Most methods of R(s) compensation become unstable at high bandwidth, making them hard to use. We describe a novel method of R(s) compensation that overcomes the stability limitations of standard designs. This method uses a state estimator, implemented with analog computation, to compute the membrane potential, V(m), which is then used in a feedback loop to implement a voltage clamp; we refer to this as state estimator R(s) compensation. To demonstrate the utility of this approach, we built an amplifier incorporating state estimator R(s) compensation. In benchtop tests, our amplifier showed significantly higher bandwidths and improved stability when compared with a commercially available amplifier. We demonstrated that state estimator R(s) compensation works well in practice by recording voltage-gated Na(+) currents under voltage-clamp conditions from dissociated neonatal rat sympathetic neurons. We conclude that state estimator R(s) compensation should make it easier to measure large rapid ionic currents with whole-cell patch-clamp techniques. PMID:10545359

Label-free electrical quantification of amplified nucleic acids through nanofluidic diodes.

PubMed

Liu, Yifan; Yobas, Levent

2013-12-15

A label-free method of quantifying nucleic acids in polymerase chain reaction (PCR) is described and could be the basis for miniaturized devices that can amplify and detect target nucleic acids in real time. The method takes advantage of ionic current rectification effect discovered in nanofluidic channels exhibiting a broken symmetry in electrochemical potential - nanofluidic diodes. Nanofluidic diodes are prototyped here on nanopipettes readily pulled from individual thin-walled glass capillaries for a proof of concept demonstration yet the basic concept would be applicable to ionic rectifiers constructed through other means. When a nanopipette modified in the tip region with cationic polyelectrolytes is presented with an unpurified PCR product, the tip surface electrostatically interacts with the amplicons and modulates its ionic rectification direction in response to the intrinsic charge of those adsorbed. Modulations are gradual and correlate well with the mass concentration of the amplicons above 2.5 ng/μL, rather than their sizes, with adequate discrimination against the background. Moreover, the tip surface, following a measurement, is regenerated through a layer-by-layer assembly of cationic polyelectrolytes and amplicons. The regenerated tips are capable of measuring distinct mass concentrations without signs of noticeable degradation in sensitivity. Further, the tips are shown capable of reproducing the amplification curve of real-time PCR through sequential steps of surface regeneration and simple electrical readout during the intermediate reaction stages. This suggests that nanopipettes as nanofluidic diodes are at a capacity to be employed for monitoring the PCR progress. Copyright © 2013 Elsevier B.V. All rights reserved.

Simulation studies of ionic liquids: Orientational correlations and static dielectric properties

NASA Astrophysics Data System (ADS)

Schröder, C.; Rudas, T.; Steinhauser, O.

2006-12-01

The ionic liquids BMIM+I-, BMIM+BF4-, and BMIM+PF6- were simulated by means of the molecular dynamics method over a time period of more than 100ns. Besides the common structural analysis, e.g., radial distribution functions and three dimensional occupancy plots, a more sophisticated orientational analysis was performed. The angular correlation functions g00110(r) and g00101(r) are the first distance dependent coefficients of the pairwise orientational distribution function g(rij,Ω1,Ω2,Ω12). These functions help to interpret the three dimensional plot and reveal interesting insights into the local structure of the analyzed ionic liquids. Furthermore, the collective network of ionic liquids can be characterized by the Kirkwood factor Gκ(r ) [J. Chem. Phys. 7, 911 (1939)]. The short-range behavior (r<10Å) of this factor may be suitable to predict the water miscibility of the ionic liquid. The long-range limit of Gk∞ is below 1 which demonstrates the strongly coupled nature of the ionic liquid networks. In addition, this factor relates the orientational structure and the dielectric properties of the ionic liquids. The static dielectric constant ɛ(ω =0) for the simulated system is 8.9-9.5. Since in ionic liquids the very same molecule contributes to the total dipole moment as well as carries a net charge, a small, but significant contribution of the cross term between the total dipole moment and the electric current to ɛ(ω =0) is observed.

Asymmetric ion transport through ion-channel-mimetic solid-state nanopores.

PubMed

Guo, Wei; Tian, Ye; Jiang, Lei

2013-12-17

Both scientists and engineers are interested in the design and fabrication of synthetic nanofluidic architectures that mimic the gating functions of biological ion channels. The effort to build such structures requires interdisciplinary efforts at the intersection of chemistry, materials science, and nanotechnology. Biological ion channels and synthetic nanofluidic devices have some structural and chemical similarities, and therefore, they share some common features in regulating the traverse ionic flow. In the past decade, researchers have identified two asymmetric ion transport phenomena in synthetic nanofluidic structures, the rectified ionic current and the net diffusion current. The rectified ionic current is a diode-like current-voltage response that occurs when switching the voltage bias. This phenomenon indicates a preferential direction of transport in the nanofluidic system. The net diffusion current occurs as a direct product of charge selectivity and is generated from the asymmetric diffusion through charged nanofluidic channels. These new ion transport phenomena and the elaborate structures that occur in biology have inspired us to build functional nanofluidic devices for both fundamental research and practical applications. In this Account, we review our recent progress in the design and fabrication of biomimetic solid-state nanofluidic devices with asymmetric ion transport behavior. We demonstrate the origin of the rectified ionic current and the net diffusion current. We also identify several influential factors and discuss how to build these asymmetric features into nanofluidic systems by controlling (1) nanopore geometry, (2) surface charge distribution, (3) chemical composition, (4) channel wall wettability, (5) environmental pH, (6) electrolyte concentration gradient, and (7) ion mobility. In the case of the first four features, we build these asymmetric features directly into the nanofluidic structures. With the final three, we construct different environmental conditions in the electrolyte solutions on either side of the nanochannel. The novel and well-controlled nanofluidic phenomena have become the foundation for many promising applications, and we have highlighted several representative examples. Inspired by the electrogenic cell of the electric eel, we have demonstrated a proof-of-concept nanofluidic reverse electrodialysis system (NREDS) that converts salinity gradient energy into electricity by means of net diffusion current. We have also constructed chirality analysis systems into nanofluidic architectures and monitored these sensing events as the change in the degree of ionic current rectification. Moreover, we have developed a biohybrid nanosystem, in which we reconstituted the F0F1-ATPase on a liposome-coated, solid-state nanoporous membrane. By applying a transmembrane proton concentration gradient, the biohybrid nanodevice can synthesize ATP in vitro. These findings have improved our understanding of the asymmetric ion transport phenomena in synthetic nanofluidic systems and offer innovative insights into the design of functional nanofluidic devices.

Simulation analysis of receptive-field size of retinal horizontal cells by ionic current model.

PubMed

Aoyama, Toshihiro; Kamiyama, Yoshimi; Usui, Shiro

2005-01-01

The size of the receptive field of retinal horizontal cells changes with the state of dark/light adaptation. We have used a mathematical model to determine how changes in the membrane conductance affect the receptive-field properties of horizontal cells. We first modeled the nonlinear membrane properties of horizontal cells based on ionic current mechanisms. The dissociated horizontal cell model reproduced the voltage-current (V-I) relationships for various extracellular glutamate concentrations measured in electrophysiological studies. Second, a network horizontal cell model was also described, and it reproduced the V-I relationship observed in vivo. The network model showed a bell-shaped relationship between the receptive-field size and constant glutamate concentration. The simulated results suggest that the calcium current is a candidate for the bell-shaped length constant relationship.

The What and Where of Adding Channel Noise to the Hodgkin-Huxley Equations

PubMed Central

Goldwyn, Joshua H.; Shea-Brown, Eric

2011-01-01

Conductance-based equations for electrically active cells form one of the most widely studied mathematical frameworks in computational biology. This framework, as expressed through a set of differential equations by Hodgkin and Huxley, synthesizes the impact of ionic currents on a cell's voltage—and the highly nonlinear impact of that voltage back on the currents themselves—into the rapid push and pull of the action potential. Later studies confirmed that these cellular dynamics are orchestrated by individual ion channels, whose conformational changes regulate the conductance of each ionic current. Thus, kinetic equations familiar from physical chemistry are the natural setting for describing conductances; for small-to-moderate numbers of channels, these will predict fluctuations in conductances and stochasticity in the resulting action potentials. At first glance, the kinetic equations provide a far more complex (and higher-dimensional) description than the original Hodgkin-Huxley equations or their counterparts. This has prompted more than a decade of efforts to capture channel fluctuations with noise terms added to the equations of Hodgkin-Huxley type. Many of these approaches, while intuitively appealing, produce quantitative errors when compared to kinetic equations; others, as only very recently demonstrated, are both accurate and relatively simple. We review what works, what doesn't, and why, seeking to build a bridge to well-established results for the deterministic equations of Hodgkin-Huxley type as well as to more modern models of ion channel dynamics. As such, we hope that this review will speed emerging studies of how channel noise modulates electrophysiological dynamics and function. We supply user-friendly MATLAB simulation code of these stochastic versions of the Hodgkin-Huxley equations on the ModelDB website (accession number 138950) and http://www.amath.washington.edu/~etsb/tutorials.html. PMID:22125479

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

Human-induced pluripotent stem cell-derived cardiomyocytes from cardiac progenitor cells: effects of selective ion channel blockade.

PubMed

Altomare, Claudia; Pianezzi, Enea; Cervio, Elisabetta; Bolis, Sara; Biemmi, Vanessa; Benzoni, Patrizia; Camici, Giovanni G; Moccetti, Tiziano; Barile, Lucio; Vassalli, Giuseppe

2016-12-01

Human-induced pluripotent stem cell (hiPSC)-derived cardiomyocytes are likely to revolutionize electrophysiological approaches to arrhythmias. Recent evidence suggests the somatic cell origin of hiPSCs may influence their differentiation potential. Owing to their cardiomyogenic potential, cardiac-stromal progenitor cells (CPCs) are an interesting cellular source for generation of hiPSC-derived cardiomyocytes. The effect of ionic current blockade in hiPSC-derived cardiomyocytes generated from CPCs has not been characterized yet. Human-induced pluripotent stem cell-derived cardiomyocytes were generated from adult CPCs and skin fibroblasts from the same individuals. The effect of selective ionic current blockade on spontaneously beating hiPSC-derived cardiomyocytes was assessed using multi-electrode arrays. Cardiac-stromal progenitor cells could be reprogrammed into hiPSCs, then differentiated into hiPSC-derived cardiomyocytes. Human-induced pluripotent stem cell-derived cardiomyocytes of cardiac origin showed higher upregulation of cardiac-specific genes compared with those of fibroblastic origin. Human-induced pluripotent stem cell-derived cardiomyocytes of both somatic cell origins exhibited sensitivity to tetrodotoxin, a blocker of Na +  current (I Na ), nifedipine, a blocker of L-type Ca 2+  current (I CaL ), and E4031, a blocker of the rapid component of delayed rectifier K +  current (I Kr ). Human-induced pluripotent stem cell-derived cardiomyocytes of cardiac origin exhibited sensitivity to JNJ303, a blocker of the slow component of delayed rectifier K +  current (I Ks ). In hiPSC-derived cardiomyocytes of cardiac origin, I Na , I CaL , I Kr , and I Ks were present as tetrodotoxin-, nifedipine-, E4031-, and JNJ303-sensitive currents, respectively. Although cardiac differentiation efficiency was improved in hiPSCs of cardiac vs. non-cardiac origin, no major functional differences were observed between hiPSC-derived cardiomyocytes of different somatic cell origins. Further studies are warranted to characterize electrophysiological properties of hiPSC-derived cardiomyocytes generated from CPCs. Published on behalf of the European Society of Cardiology. All rights reserved. © The Author 2016. For Permissions, please email: journals.permissions@oup.com.

Synthesis and Characterization of Ionically Crosslinked Elastomers

DTIC Science & Technology

2015-05-12

SECURITY CLASSIFICATION OF: In this research poly(n-butyl acrylate) (PBA) elastomers were investigated as model systems to study the thermomechanical...subject to any oenalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO...Ionically Crosslinked Elastomers Report Title In this research poly(n-butyl acrylate) (PBA) elastomers were investigated as model systems to study the

Porous dendritic copper: an electrocatalyst for highly selective CO2 reduction to formate in water/ionic liquid electrolyte.

PubMed

Huan, Tran Ngoc; Simon, Philippe; Rousse, Gwenaëlle; Génois, Isabelle; Artero, Vincent; Fontecave, Marc

2017-01-01

Copper is currently extensively studied because it provides promising electrodes for carbon dioxide electroreduction. The original combination, reported here, of a nanostructured porous dendritic Cu-based material, characterized by electron microcopy (SEM, TEM) and X-ray diffraction methods, and a water/ionic liquid mixture as the solvent, contributing to CO 2 solubilization and activation, results in a remarkably efficient (large current densities at low overpotentials), stable and selective (large faradic yields) electrocatalytic system for the conversion of CO 2 into formic acid, a product with a variety of uses. These results provide new directions for the further improvement of Cu electrodes.

Nonlinear space charge dynamics in mixed ionic-electronic conductors: Resistive switching and ferroelectric-like hysteresis of electromechanical response

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

Morozovska, Anna N.; Morozovsky, Nicholas V.; Eliseev, Eugene A.

We performed self-consistent modelling of nonlinear electrotransport and electromechanical response of thin films of mixed ionic-electronic conductors (MIEC) allowing for steric effects of mobile charged defects (ions, protons, or vacancies), electron degeneration, and Vegard stresses. We establish correlations between the features of the nonlinear space-charge dynamics, current-voltage, and bending-voltage curves for different types of the film electrodes. A pronounced ferroelectric-like hysteresis of the bending-voltage loops and current maxima on the double hysteresis current-voltage loops appear for the electron-transport electrodes. The double hysteresis loop with pronounced humps indicates a memristor-type resistive switching. The switching occurs due to the strong nonlinear couplingmore » between the electronic and ionic subsystems. A sharp meta-stable maximum of the electron density appears near one open electrode and moves to another one during the periodic change of applied voltage. Our results can explain the nonlinear nature and correlation of electrical and mechanical memory effects in thin MIEC films. The analytical expression proving that the electrically induced bending of MIEC films can be detected by interferometric methods is derived.« less

Detection beyond the Debye screening length in a high-frequency nanoelectronic biosensor.

PubMed

Kulkarni, Girish S; Zhong, Zhaohui

2012-02-08

Nanosensors based on the unique electronic properties of nanotubes and nanowires offer high sensitivity and have the potential to revolutionize the field of Point-of-Care (POC) medical diagnosis. The direct current (dc) detection of a wide array of organic and inorganic molecules has been demonstrated on these devices. However, sensing mechanism based on measuring changes in dc conductance fails at high background salt concentrations, where the sensitivity of the devices suffers from the ionic screening due to mobile ions present in the solution. Here, we successfully demonstrate that the fundamental ionic screening effect can be mitigated by operating single-walled carbon nanotube field effect transistor as a high-frequency biosensor. The nonlinear mixing between the alternating current excitation field and the molecular dipole field can generate mixing current sensitive to the surface-bound biomolecules. Electrical detection of monolayer streptavidin binding to biotin in 100 mM buffer solution is achieved at a frequency beyond 1 MHz. Theoretical modeling confirms improved sensitivity at high frequency through mitigation of the ionic screening effect. The results should promise a new biosensing platform for POC detection, where biosensors functioning directly in physiologically relevant condition are desired. © 2012 American Chemical Society

Multifunctional nanopipette for simultaneous ionic current and potential detection of nanoparticles

NASA Astrophysics Data System (ADS)

Panday, Namuna; He, Jin

Nanopipette has been demonstrated as a nanopore type biosensor for DNA, protein, nanoparticle and virus analysis. In the last two decades, nanopore based technologies have made remarkable progress for single entity detection and analysis. Multifunctional nanopipette for multi-parameter detection is a new trend for nanopore based technique. We have developed a technique to fabricate multifunctional nanopipette which contains both nanopore and carbon nanoelectrode (CNE) at the nanopipette tip. It can be quickly, cheaply and reproducibly fabricated from theta pipettes. We have been able to use this multifunctional nanopieptte for simultaneous detection of ionic current and local electrical potential changes during translocation of charged gold nanoparticles (GNPs) which is used as a model experiment. The CNE functions as a local potential probe. We have demonstrated that it can detect the local potential change during translocation of a single GNP as well as collective potential change due to cluster of GNPs outside the nanopore entrance. From the potential change, we can also have insight of motion of GNPs before entering the nanopore. We have also tested insulating and biological NPs with various size and charge. Observed results have shown correlations between ionic current and potential change during translocation of these NPs. Florida International University.

Spectrum of antimicrobial activity associated with ionic colloidal silver.

PubMed

Morrill, Kira; May, Kathleen; Leek, Daniel; Langland, Nicole; Jeane, La Deana; Ventura, Jose; Skubisz, Corey; Scherer, Sean; Lopez, Eric; Crocker, Ephraim; Peters, Rachel; Oertle, John; Nguyen, Krystine; Just, Scott; Orian, Michael; Humphrey, Meaghan; Payne, David; Jacobs, Bertram; Waters, Robert; Langland, Jeffrey

2013-03-01

Silver has historically and extensively been used as a broad-spectrum antimicrobial agent. However, the Food and Drug Administration currently does not recognize colloidal silver as a safe and effective antimicrobial agent. The goal of this study was to further evaluate the antimicrobial efficacy of colloidal silver. Several strains of bacteria, fungi, and viruses were grown under multicycle growth conditions in the presence or absence of ionic colloidal silver in order to assess the antimicrobial activity. For bacteria grown under aerobic or anaerobic conditions, significant growth inhibition was observed, although multiple treatments were typically required. For fungal cultures, the effects of ionic colloidal silver varied significantly between different genera. No viral growth inhibition was observed with any strains tested. The study data support ionic colloidal silver as a broad-spectrum antimicrobial agent against aerobic and anaerobic bacteria, while having a more limited and specific spectrum of activity against fungi.

Composite polarizability and the construction of an invariant function of refraction and mass density for solutions.

PubMed

Szymański, Krzysztof; Petrache, Horia I

2011-04-14

Re-examination of dynamical ionic polarizabilities in water solutions leads to the formulation of a solution function r(c), which combines the indices of refraction and mass densities of solutions. We show that this function should be independent of ionic concentration if the composite polarizabilities of hydrated solute clusters are constant. Using existing experimental data for a number of aqueous salt and organic solutions, we find that the r(c) function is either constant or varies linearly with concentration, in most cases with negligible slope. We use this function to compare ionic polarizabilities of crystals and aqueous solutions and to highlight how solute polarizabilities at infinite dilution scale with the electronic valence shell of cations and anions. The proposed r(c) function can be used generally to verify the consistency of experimental measurements and of simulation results, and it provides a test of assumptions in current theories of ionic polarizabilities.

Hydrogen Sulfide and Ionic Liquids: Absorption, Separation, and Oxidation.

PubMed

Chiappe, Cinzia; Pomelli, Christian Silvio

2017-06-01

Economical and environmental concerns are the main motivations for development of energy-efficient processes and new eco-friendly materials for the capture of greenhouse gases. Currently, H 2 S capture is dominated by physical and/or chemical absorption technologies, which are, however, energy intensive and often problematic from an environmental point of view due to emission of volatile solvent components. Ionic liquids have been proposed as a promising alternative to conventional solvents because of their low volatility and other interesting properties. The aim of the present review paper is to provide a detailed overview of the achievements and difficulties that have been encountered in finding suitable ionic liquids for H 2 S capture. The effect of ionic liquid anions, cations, and functional groups on the H 2 S absorption, separation, and oxidation are highlighted. Recent developments on yet scarcely available molecular simulations and on the development of robust predictive methods are also discussed.

Electrochemical Polishing Applications and EIS of a Novel Choline Chloride-Based Ionic Liquid

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Minimal surface roughness is a critical feature for high-field superconducting radio frequency (SRF) cavities used to engineer particle accelerators. Current methods for polishing Niobium cavities typically utilize solutions containing a mixture of concentrated sulfuric and hydrofluoric acid. Polishing processes such as these are effective, yet there are many hazards and costs associated with the use (and safe disposal) of the concentrated acid solutions. An alternative method for electrochemical polishing of the cavities was explored using a novel ionic liquid solution containing choline chloride. Potentiostatic electrochemical impedance spectroscopy (EIS) was used to analyze the ionic polishing solution. Final surface roughness ofmore » the Nb was found to be comparable to that of the acid-polishing method, as assessed by atomic force microscopy (AFM). This indicates that ionic liquid-based electrochemical polishing of Nb is a viable replacement for acid-based methods for preparation of SRF cavities.« less

Electrophysiological heterogeneity of pacemaker cells in the rabbit intercaval region, including the SA node: insights from recording multiple ion currents in each cell.

PubMed

Monfredi, Oliver; Tsutsui, Kenta; Ziman, Bruce; Stern, Michael D; Lakatta, Edward G; Maltsev, Victor A

2018-03-01

Cardiac pacemaker cells, including cells of the sinoatrial node, are heterogeneous in size, morphology, and electrophysiological characteristics. The exact extent to which these cells differ electrophysiologically is unclear yet is critical to understanding their functioning. We examined major ionic currents in individual intercaval pacemaker cells (IPCs) sampled from the paracristal, intercaval region (including the sinoatrial node) that were spontaneously beating after enzymatic isolation from rabbit hearts. The beating rate was measured at baseline and after inhibition of the Ca 2+ pump with cyclopiazonic acid. Thereafter, in each cell, we consecutively measured the density of funny current ( I f ), delayed rectifier K + current ( I K ) (a surrogate of repolarization capacity), and L-type Ca 2+ current ( I Ca,L ) using whole cell patch clamp . The ionic current densities varied to a greater extent than previously appreciated, with some IPCs demonstrating very small or zero I f . The density of none of the currents was correlated with cell size, while I Ca,L and I f densities were related to baseline beating rates. I f density was correlated with I K density but not with that of I Ca,L . Inhibition of Ca 2+ cycling had a greater beating rate slowing effect in IPCs with lower I f densities. Our numerical model simulation indicated that 1) IPCs with small (or zero) I f or small I Ca,L can operate via a major contribution of Ca 2+ clock, 2) I f -Ca 2+ -clock interplay could be important for robust pacemaking function, and 3) coupled I f - I K function could regulate maximum diastolic potential. Thus, we have demonstrated marked electrophysiological heterogeneity of IPCs. This heterogeneity is manifested in basal beating rate and response to interference of Ca 2+ cycling, which is linked to I f . NEW & NOTEWORTHY In the present study, a hitherto unrecognized range of heterogeneity of ion currents in pacemaker cells from the intercaval region is demonstrated. Relationships between basal beating rate and L-type Ca 2+ current and funny current ( I f ) density are uncovered, along with a positive relationship between I f and delayed rectifier K + current. Links are shown between the response to Ca 2+ cycling blockade and I f density.

Measuring the proton selectivity of graphene membranes

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

Walker, Michael I.; Keyser, Ulrich F., E-mail: ufk20@cam.ac.uk; Braeuninger-Weimer, Philipp

2015-11-23

By systematically studying the proton selectivity of free-standing graphene membranes in aqueous solutions, we demonstrate that protons are transported by passing through defects. We study the current-voltage characteristics of single-layer graphene grown by chemical vapour deposition (CVD) when a concentration gradient of HCl exists across it. Our measurements can unambiguously determine that H{sup +} ions are responsible for the selective part of the ionic current. By comparing the observed reversal potentials with positive and negative controls, we demonstrate that the as-grown graphene is only weakly selective for protons. We use atomic layer deposition to block most of the defects inmore » our CVD graphene. Our results show that a reduction in defect size decreases the ionic current but increases proton selectivity.« less

Electrohydrodynamic ionic wind, force field, and ionic mobility in a positive dc wire-to-cylinders corona discharge in air

NASA Astrophysics Data System (ADS)

Monrolin, Nicolas; Praud, Olivier; Plouraboué, Franck

2018-06-01

Ionic wind refers to the acceleration of partially ionized air between two high-voltage electrodes. We study the momentum transfer from ions to air, resulting from ionic wind created by two asymmetric electrodes and producing a net thrust. This electrohydrodynamic (EHD) thrust, has already been measured in previous studies with digital scales. In this study, we provide more insights into the electrohydrodynamic momentum transfer for a wire-to-cylinder(s) positive dc corona discharge. We provide a simple and general theoretical derivation for EHD thrust, which is proportional to the current/mobility ratio and also to an effective distance integrated on the surface of the electrodes. By considering various electrode configurations, our investigation brings out the physical origin of previously obtained optimal configurations, associated with a better tradeoff between Coulomb forcing, friction occurring at the collector, and wake interactions. By measuring two-dimensional velocity fields using particle image velocimetry (PIV), we are able to evaluate the resulting local net force, including the pressure gradient. It is shown that the contribution of velocity fluctuations in the wake of the collecting electrode(s) must be taken into account to recover the net thrust. We confirm the proportionality between the EHD force and the current/mobility ratio experimentally, and evaluate the ion mobility from PIV measurements. A spectral analysis of the velocity fluctuations indicates a dominant frequency corresponding to a Strouhal number of 0.3 based on the ionic wind velocity and the collector size. Finally, the effective mobility of charge carriers is estimated by a PIV based method inside the drift region.

Ionic current and polarization effect in TlBr

NASA Astrophysics Data System (ADS)

Leão, Cedric Rocha; Lordi, Vincenzo

2013-02-01

Thallium bromide (TlBr) is an ionic semiconductor that has shown great capacity for accurate radiation detection. Its application to this end, however, has been hampered by degradation of performance over time, in a process called polarization. This effect has been traditionally assigned to a build-up of ions at the electrodes, which would counteract an applied electrical bias field. Here, we estimate the ionic mobility in TlBr and its possible association with the polarization effect using parameter-free quantum simulations. Our results indicate that in samples with up to moderate levels of impurities, ions cannot traverse distances large enough to generate zones of accumulation and depletion in the crystal, suggesting different causes for the polarization effect.

cGMP and cyclic nucleotide-gated channels participate in mouse sperm capacitation.

PubMed

Cisneros-Mejorado, Abraham; Sánchez Herrera, Daniel P

2012-01-20

During capacitation of mammalian sperm intracellular [Ca(2+)] and cyclic nucleotides increase, suggesting that CNG channels play a role in the physiology of sperm. Here we study the effect of capacitation, 8Br-cAMP (8-bromoadenosine 3',5'-cyclic monophosphate) and 8Br-cGMP (8-bromoguanosine 3',5'-cyclic monophosphate) on the macroscopic ionic currents of mouse sperm, finding the existence of different populations of sperm, in terms of the recorded current and its response to cyclic nucleotides. Our results show that capacitation and cyclic nucleotides increase the ionic current, having a differential sensitivity to cGMP (cyclic guanosine monophosphate) and cAMP (cyclic adenosine monophosphate). Using a specific inhibitor we determine the contribution of CNG channels to macroscopic current and capacitation. Copyright © 2011 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

Ionic channels underlying the ventricular action potential in zebrafish embryo.

PubMed

Alday, Aintzane; Alonso, Hiart; Gallego, Monica; Urrutia, Janire; Letamendia, Ainhoa; Callol, Carles; Casis, Oscar

2014-06-01

Over the last years zebrafish has become a popular model in the study of cardiac physiology, pathology and pharmacology. Recently, the application of the 3Rs regulation and the characteristics of the embryo have reduced the use of adult zebrafish use in many studies. However, the zebrafish embryo cardiac physiology is poorly characterized since most works have used indirect techniques and direct recordings of cardiac action potential and ionic currents are scarce. In order to optimize the zebrafish embryo model, we used electrophysiological, pharmacological and immunofluorescence tools to identify the characteristics and the ionic channels involved in the ventricular action potentials of zebrafish embryos. The application of Na(+) or T-type Ca(+2) channel blockers eliminated the cardiac electrical activity, indicating that the action potential upstroke depends on Na(+) and T-type Ca(+2) currents. The plateau phase depends on L-type Ca(+2) channels since it is abolished by specific blockade. The direct channel blockade indicates that the action potential repolarization and diastolic potential depends on ERG K(+) channels. The presence in the embryonic heart of the Nav1.5, Cav1.2, Cav3.2 and ERG channels was also confirmed by immunofluorescence, while the absence of effect of specific blockers and immunostaining indicate that two K(+) repolarizing currents present in human heart, Ito and IKs, are absent in the embryonic zebrafish heart. Our results describe the ionic channels present and its role in the zebrafish embryo heart and support the use of zebrafish embryos to study human diseases and their use for drug testing. Copyright © 2014 Elsevier Ltd. All rights reserved.

Interaction of proteins with ionic liquid, alcohol and DMSO and in situ generation of gold nano-clusters in a cell.

PubMed

Nandi, Somen; Parui, Sridip; Halder, Ritaban; Jana, Biman; Bhattacharyya, Kankan

2018-06-01

In this review, we give a brief overview on how the interaction of proteins with ionic liquids, alcohols and dimethyl sulfoxide (DMSO) influences the stability, conformational dynamics and function of proteins/enzymes. We present experimental results obtained from fluorescence correlation spectroscopy on the effect of ionic liquid or alcohol or DMSO on the size (more precisely, the diffusion constant) and conformational dynamics of lysozyme, cytochrome c and human serum albumin in aqueous solution. The interaction of ionic liquid with biomolecules (e.g. protein, DNA etc.) has emerged as a current frontier. We demonstrate that ionic liquids are excellent stabilizers of protein and DNA and, in some cases, cause refolding of a protein already denatured by chemical denaturing agents. We show that in ethanol-water binary mixture, proteins undergo non-monotonic changes in size and dynamics with increasing ethanol content. We also discuss the effect of water-DMSO mixture on the stability of proteins. We demonstrate how large-scale molecular dynamics simulations have revealed the molecular origin of this observed phenomenon and provide a microscopic picture of the immediate environment of the biomolecules. Finally, we describe how favorable interactions of ionic liquids may be utilized for in situ generation of fluorescent gold nano-clusters for imaging a live cell.

Block Copolymers and Ionic Liquids: A New Class of Functional Nanocomposites

NASA Astrophysics Data System (ADS)

Lodge, Timothy

2009-03-01

Block copolymers provide a remarkably versatile platform for achieving desired nanostructures by self-assembly, with lengthscales varying from a few nanometers up to several hundred nanometers. Ionic liquids are an emerging class of solvents, with an appealing set of physical attributes. These include negligible vapor pressure, high chemical and thermal stability, tunable solvation properties, high ionic conductivity, and wide electrochemical windows. For various applications it will be necessary to solidify the ionic liquid into particular spatial arrangements, such as membranes or gels, or to partition the ionic liquid in coexisting phases, such as microemulsions and micelles. One example includes formation of spherical, cylindrical, and vesicular micelles by poly(butadiene-b-ethylene oxide) and poly(styrene-b-methylmethacrylate) in the common hydrophobic ionic liquids [BMI][PF6] and [EMI][TFSI]. This work has been extended to the formation of reversible micelle shuttles between ionic liquids and water, whereby entire micelles transfer from one phase to the other, reversibly, depending on temperature and solvent quality. Formation of ion gels has been achieved by self-assembly of poly(styrene-b-ethylene oxide-b-styrene) triblocks in ionic liquids, and by the thermoreversible system poly(N-isopropylacrylamide-b-ethylene oxide-b-N-isopropylacrylamide), using as little as 4% copolymer. Further, these gels have been shown to be remarkably effective as gate dielectrics in organic thin film transistors. The remarkably high capacitance of the ion gels (> 10 μF/cm^2) supports a very high carrier density in an organic semiconductor such as poly(3-hexylthiophene), leading to milliamp currents for low applied voltages. Furthermore, the rapid mobility of the ions enables switching speeds approaching 10 kHz, orders of magnitude higher than achievable with other polymer-based dielectrics such as PEO/LiClO4. Finally, we have shown that ordered nanostructures of block copolymers plus ionic liquids show the characteristic self-assembly properties of strongly-segregated systems. Prospects for anisotropic ionic conductivity are also being explored.

Free Fatty Acid Effects on the Atrial Myocardium: Membrane Ionic Currents Are Remodeled by the Disruption of T-Tubular Architecture

PubMed Central

O’Connell, Ryan P.; Musa, Hassan; Gomez, Mario San Martin; Avula, Uma Mahesh; Herron, Todd J.; Kalifa, Jerome; Anumonwo, Justus M. B.

2015-01-01

Background Epicardial adiposity and plasma levels of free fatty acids (FFAs) are elevated in atrial fibrillation, heart failure and obesity, with potentially detrimental effects on myocardial function. As major components of epicardial fat, FFAs may be abnormally regulated, with a potential to detrimentally modulate electro-mechanical function. The cellular mechanisms underlying such effects of FFAs are unknown. Objective To determine the mechanisms underlying electrophysiological effects of palmitic (PA), stearic (SA) and oleic (OA) FFAs on sheep atrial myocytes. Methods We used electrophysiological techniques, numerical simulations, biochemistry and optical imaging to examine the effects of acutely (≤ 15 min), short-term (4–6 hour) or 24-hour application of individual FFAs (10 μM) on isolated ovine left atrial myocytes (LAMs). Results Acute and short-term incubation in FFAs resulted in no differences in passive or active properties of isolated left atrial myocytes (LAMs). 24-hour application had differential effects depending on the FFA. PA did not affect cellular passive properties but shortened (p<0.05) action potential duration at 30% repolarization (APD30). APD50 and APD80 were unchanged. SA had no effect on resting membrane potential but reduced membrane capacitance by 15% (p<0.05), and abbreviated APD at all values measured (p≤0.001). OA did not significantly affect passive or active properties of LAMs. Measurement of the major voltage-gated ion channels in SA treated LAMs showed a ~60% reduction (p<0.01) of the L-type calcium current (ICa-L) and ~30% reduction (p<0.05) in the transient outward potassium current (ITO). A human atrial cell model recapitulated SA effects on APD. Optical imaging showed that SA incubated for 24 hours altered t-tubular structure in isolated cells (p<0.0001). Conclusions SA disrupts t-tubular architecture and remodels properties of membrane ionic currents in sheep atrial myocytes, with potential implications in arrhythmogenesis. PMID:26274906

Free Fatty Acid Effects on the Atrial Myocardium: Membrane Ionic Currents Are Remodeled by the Disruption of T-Tubular Architecture.

PubMed

O'Connell, Ryan P; Musa, Hassan; Gomez, Mario San Martin; Avula, Uma Mahesh; Herron, Todd J; Kalifa, Jerome; Anumonwo, Justus M B

2015-01-01

Epicardial adiposity and plasma levels of free fatty acids (FFAs) are elevated in atrial fibrillation, heart failure and obesity, with potentially detrimental effects on myocardial function. As major components of epicardial fat, FFAs may be abnormally regulated, with a potential to detrimentally modulate electro-mechanical function. The cellular mechanisms underlying such effects of FFAs are unknown. To determine the mechanisms underlying electrophysiological effects of palmitic (PA), stearic (SA) and oleic (OA) FFAs on sheep atrial myocytes. We used electrophysiological techniques, numerical simulations, biochemistry and optical imaging to examine the effects of acutely (≤ 15 min), short-term (4-6 hour) or 24-hour application of individual FFAs (10 μM) on isolated ovine left atrial myocytes (LAMs). Acute and short-term incubation in FFAs resulted in no differences in passive or active properties of isolated left atrial myocytes (LAMs). 24-hour application had differential effects depending on the FFA. PA did not affect cellular passive properties but shortened (p<0.05) action potential duration at 30% repolarization (APD30). APD50 and APD80 were unchanged. SA had no effect on resting membrane potential but reduced membrane capacitance by 15% (p<0.05), and abbreviated APD at all values measured (p≤0.001). OA did not significantly affect passive or active properties of LAMs. Measurement of the major voltage-gated ion channels in SA treated LAMs showed a ~60% reduction (p<0.01) of the L-type calcium current (ICa-L) and ~30% reduction (p<0.05) in the transient outward potassium current (ITO). A human atrial cell model recapitulated SA effects on APD. Optical imaging showed that SA incubated for 24 hours altered t-tubular structure in isolated cells (p<0.0001). SA disrupts t-tubular architecture and remodels properties of membrane ionic currents in sheep atrial myocytes, with potential implications in arrhythmogenesis.

Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions

NASA Astrophysics Data System (ADS)

Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G.; Qiao, Rui

2014-07-01

We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

PubMed

Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

2014-07-16

We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Modeling regulation of cardiac KATP and L-type Ca2+ currents by ATP, ADP, and Mg2+.

PubMed

Michailova, Anushka; Saucerman, Jeffrey; Belik, Mary Ellen; McCulloch, Andrew D

2005-03-01

Changes in cytosolic free Mg(2+) and adenosine nucleotide phosphates affect cardiac excitability and contractility. To investigate how modulation by Mg(2+), ATP, and ADP of K(ATP) and L-type Ca(2+) channels influences excitation-contraction coupling, we incorporated equations for intracellular ATP and MgADP regulation of the K(ATP) current and MgATP regulation of the L-type Ca(2+) current in an ionic-metabolic model of the canine ventricular myocyte. The new model: 1), quantitatively reproduces a dose-response relationship for the effects of changes in ATP on K(ATP) current, 2), simulates effects of ADP in modulating ATP sensitivity of K(ATP) channel, 3), predicts activation of Ca(2+) current during rapid increase in MgATP, and 4), demonstrates that decreased ATP/ADP ratio with normal total Mg(2+) or increased free Mg(2+) with normal ATP and ADP activate K(ATP) current, shorten action potential, and alter ionic currents and intracellular Ca(2+) signals. The model predictions are in agreement with experimental data measured under normal and a variety of pathological conditions.

Modeling regulation of cardiac KATP and L-type Ca2+ currents by ATP, ADP, and Mg2+

NASA Technical Reports Server (NTRS)

Michailova, Anushka; Saucerman, Jeffrey; Belik, Mary Ellen; McCulloch, Andrew D.

2005-01-01

Changes in cytosolic free Mg(2+) and adenosine nucleotide phosphates affect cardiac excitability and contractility. To investigate how modulation by Mg(2+), ATP, and ADP of K(ATP) and L-type Ca(2+) channels influences excitation-contraction coupling, we incorporated equations for intracellular ATP and MgADP regulation of the K(ATP) current and MgATP regulation of the L-type Ca(2+) current in an ionic-metabolic model of the canine ventricular myocyte. The new model: 1), quantitatively reproduces a dose-response relationship for the effects of changes in ATP on K(ATP) current, 2), simulates effects of ADP in modulating ATP sensitivity of K(ATP) channel, 3), predicts activation of Ca(2+) current during rapid increase in MgATP, and 4), demonstrates that decreased ATP/ADP ratio with normal total Mg(2+) or increased free Mg(2+) with normal ATP and ADP activate K(ATP) current, shorten action potential, and alter ionic currents and intracellular Ca(2+) signals. The model predictions are in agreement with experimental data measured under normal and a variety of pathological conditions.

Electromagnetic micropores: fabrication and operation.

PubMed

Basore, Joseph R; Lavrik, Nickolay V; Baker, Lane A

2010-12-21

We describe the fabrication and characterization of electromagnetic micropores. These devices consist of a micropore encompassed by a microelectromagnetic trap. Fabrication of the device involves multiple photolithographic steps, combined with deep reactive ion etching and subsequent insulation steps. When immersed in an electrolyte solution, application of a constant potential across the micropore results in an ionic current. Energizing the electromagnetic trap surrounding the micropore produces regions of high magnetic field gradients in the vicinity of the micropore that can direct motion of a ferrofluid onto or off of the micropore. This results in dynamic gating of the ion current through the micropore structure. In this report, we detail fabrication and characterize the electrical and ionic properties of the prepared electromagnetic micropores.

Characterization of Thallium Bromide (TlBr) for Room Temperature Radiation Detectors

NASA Astrophysics Data System (ADS)

Smith, Holland McTyeire

Thallium bromide (TlBr) has emerged as a remarkably well-suited material for room temperature radiation detection. The unique combination of high-Z elements, high density, suitable band gap, and excellent electrical transport properties present in TlBr have brought device performance up to par with CdZnTe (CZT), the current market-leading room temperature radiation detector material. TlBr research is at an earlier stage than that of CZT, giving hope that the material will see even further improvement in electronic properties. Improving a resistive semiconductor material requires knowledge of deep levels present in the material and the effects of these deep levels on transport properties. Very few deep level studies have been conducted on TlBr, and none with the depth required to generate useful growth suggestions. In this dissertation, deep levels in nominally undoped and doped TlBr samples are studied with electrical and optical methods. Photo-Induced Conductivity Transient Spectroscopy (PICTS) is used to discover many deep levels in TlBr electrically. These levels are compared to sub-band gap optical transitions originating from defects observed in emission spectra. The results of this research indicate that the origin of resistivity in TlBr is likely due to deep level defects pinning the Fermi level at least ˜0.7 eV from either the conduction or valence band edge. The effect of dopants and deep levels on transport in TlBr is assessed with microwave photoconductivity decay analysis. It is found that Pb-, Se-, and O-doping decreases carrier lifetime in TlBr, whereas C-doping does not. TlBr exhibits weak ionic conductivity at room temperature, which both negatively affects the leakage current of detectors and leads to device degradation over time. Researchers are actively looking for ways to reduce or eliminate the ionic conductivity, but are faced with an intriguing challenge of materials engineering: is it possible to mitigate the ionic conduction of TlBr without harming the excellent electronic transport properties? Doping TlBr in order to control the ionic conductivity has been proposed and shown to be effective in reducing dark ionic current, but the electronic effects of the dopants has not been previously studied in detail. In this dissertation, the electronic effects of dopants introduced for ionic reasons are evaluated.

Physical properties of ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various anions and the bis(trifluoromethylsulfonyl)imide anion with various cations.

PubMed

Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F; Benesi, Alan J; Maroncelli, Mark

2008-01-10

Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

Nanopore detection of DNA molecules in crowded neutral polymer solutions

NASA Astrophysics Data System (ADS)

Sharma, Rajesh Kumar; Dai, Liang; Doyle, Patrick; Garaj, Slaven

Nanopore sensing is a precise technique for analysis of the structure and dynamics of individual biomolecules in different environments, and has even become a prominent technique for next-gen DNA sequencing. In the nanopore sensor, an individual DNA molecule is electrophoretically translocated through a single, nanometer-scaled pore in a solid-state membrane separating two chambers filled with electrolyte. The conformation of the molecule is deduced from modulations in the ionic current through the pore during the translocation event. Using nanopores, we investigated the dynamics of the DNA molecules in a crowded solution of neutral polymers of different sizes and concentrations. The translocation dynamics depends significantly on the size and concentration of the polymers, as different contributions to the electrophoretic and entropic forces on the DNA molecules come into play. This setup offers an excellent, tuneable model-system for probing biologically relevant questions regarding the behaviour of DNA molecules in highly confined and crowded environments. Singapore-MIT Alliance for Research and Technology.

Carbon/PTFE Electrode for Lithium/Air-Water Batteries

DTIC Science & Technology

2007-03-01

non-electronically conducting ceramic membrane impervious to water but with a high ionic conductivity for lithium-ions. LiTixAly(PO4)3 is one such...example of a ceramic composition that has been used in this manner. The lithium ion can be thought of as being solvated by the ceramic membrane as it...through 5) provides current. To balance the overall charge in the reaction, positive lithium ions flow 1 through an ionically conducting ceramic

Ionic liquid versus SiO 2 gated a-IGZO thin film transistors: A direct comparison

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

Pudasaini, Pushpa Raj; Noh, Joo Hyon; Wong, Anthony T.

Here, ionic liquid gated field effect transistors have been extensively studied due to their low operation voltage, ease of processing and the realization of high electric fields at low bias voltages. Here, we report ionic liquid (IL) gated thin film transistors (TFTs) based on amorphous Indium Gallium Zinc Oxide (a-IGZO) active layers and directly compare the characteristics with a standard SiO 2 gated device. The transport measurements of the top IL gated device revealed the n-channel property of the IGZO thin film with a current ON/OFF ratio ~10 5, a promising field effect mobility of 14.20 cm 2V –1s –1,more » and a threshold voltage of 0.5 V. Comparable measurements on the bottom SiO2 gate insulator revealed a current ON/OFF ratio >108, a field effect mobility of 13.89 cm 2V –1s –1 and a threshold voltage of 2.5 V. Furthermore, temperature-dependent measurements revealed that the ionic liquid electric double layer can be “frozen-in” by cooling below the glass transition temperature with an applied electrical bias. Positive and negative freezing bias locks-in the IGZO TFT “ON” and “OFF” state, respectively, which could lead to new switching and possibly non-volatile memory applications.« less

Ionic liquid versus SiO 2 gated a-IGZO thin film transistors: A direct comparison

DOE PAGES

Pudasaini, Pushpa Raj; Noh, Joo Hyon; Wong, Anthony T.; ...

2015-08-12

Here, ionic liquid gated field effect transistors have been extensively studied due to their low operation voltage, ease of processing and the realization of high electric fields at low bias voltages. Here, we report ionic liquid (IL) gated thin film transistors (TFTs) based on amorphous Indium Gallium Zinc Oxide (a-IGZO) active layers and directly compare the characteristics with a standard SiO 2 gated device. The transport measurements of the top IL gated device revealed the n-channel property of the IGZO thin film with a current ON/OFF ratio ~10 5, a promising field effect mobility of 14.20 cm 2V –1s –1,more » and a threshold voltage of 0.5 V. Comparable measurements on the bottom SiO2 gate insulator revealed a current ON/OFF ratio >108, a field effect mobility of 13.89 cm 2V –1s –1 and a threshold voltage of 2.5 V. Furthermore, temperature-dependent measurements revealed that the ionic liquid electric double layer can be “frozen-in” by cooling below the glass transition temperature with an applied electrical bias. Positive and negative freezing bias locks-in the IGZO TFT “ON” and “OFF” state, respectively, which could lead to new switching and possibly non-volatile memory applications.« less

Ionic Liquids in Biomass Processing

NASA Astrophysics Data System (ADS)

Tan, Suzie Su Yin; Macfarlane, Douglas R.

Ionic liquids have been studied for their special solvent properties in a wide range of processes, including reactions involving carbohydrates such as cellulose and glucose. Biomass is a widely available and renewable resource that is likely to become an economically viable source of starting materials for chemical and fuel production, especially with the price of petroleum set to increase as supplies are diminished. Biopolymers such as cellulose, hemicellulose and lignin may be converted to useful products, either by direct functionalisation of the polymers or depolymerisation to monomers, followed by microbial or chemical conversion to useful chemicals. Major barriers to the effective conversion of biomass currently include the high crystallinity of cellulose, high reactivity of carbohydrates and lignin, insolubility of cellulose in conventional solvents, as well as heterogeneity in the native lignocellulosic materials and in lignin itself. This combination of factors often results in highly heterogeneous depolymerisation products, which make efficient separation difficult. Thus the extraction, depolymerisation and conversion of biopolymers will require novel reaction systems in order to be both economically attractive and environmentally benign. The solubility of biopolymers in ionic liquids is a major advantage of their use, allowing homogeneous reaction conditions, and this has stimulated a growing research effort in this field. This review examines current research involving the use of ionic liquids in biomass reactions, with perspectives on how it relates to green chemistry, economic viability, and conventional biomass processes.

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

In silico simulations of experimental protocols for cardiac modeling.

PubMed

Carro, Jesus; Rodriguez, Jose Felix; Pueyo, Esther

2014-01-01

A mathematical model of the AP involves the sum of different transmembrane ionic currents and the balance of intracellular ionic concentrations. To each ionic current corresponds an equation involving several effects. There are a number of model parameters that must be identified using specific experimental protocols in which the effects are considered as independent. However, when the model complexity grows, the interaction between effects becomes increasingly important. Therefore, model parameters identified considering the different effects as independent might be misleading. In this work, a novel methodology consisting in performing in silico simulations of the experimental protocol and then comparing experimental and simulated outcomes is proposed for parameter model identification and validation. The potential of the methodology is demonstrated by validating voltage-dependent L-type calcium current (ICaL) inactivation in recently proposed human ventricular AP models with different formulations. Our results show large differences between ICaL inactivation as calculated from the model equation and ICaL inactivation from the in silico simulations due to the interaction between effects and/or to the experimental protocol. Our results suggest that, when proposing any new model formulation, consistency between such formulation and the corresponding experimental data that is aimed at being reproduced needs to be first verified considering all involved factors.

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature.

PubMed

Lin, Xinrong; Chapman Varela, Jennifer; Grinstaff, Mark W

2016-12-20

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 °C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Scanning thermo-ionic microscopy for probing local electrochemistry at the nanoscale

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

Eshghinejad, Ahmadreza; Nasr Esfahani, Ehsan; Wang, Peiqi

2016-05-28

Conventional electrochemical characterization techniques based on voltage and current measurements only probe faradaic and capacitive rates in aggregate. In this work we develop a scanning thermo-ionic microscopy (STIM) to probe local electrochemistry at the nanoscale, based on imaging of Vegard strain induced by thermal oscillation. It is demonstrated from both theoretical analysis and experimental validation that the second harmonic response of thermally induced cantilever vibration, associated with thermal expansion, is present in all solids, whereas the fourth harmonic response, caused by local transport of mobile species, is only present in ionic materials. The origin of STIM response is further confirmedmore » by its reduced amplitude with respect to increased contact force, due to the coupling of stress to concentration of ionic species and/or electronic defects. The technique has been applied to probe Sm-doped Ceria and LiFePO{sub 4}, both of which exhibit higher concentrations of mobile species near grain boundaries. The STIM gives us a powerful method to study local electrochemistry with high sensitivity and spatial resolution for a wide range of ionic systems, as well as ability to map local thermomechanical response.« less

Effects of ionic liquid to water ratio as a composite medium for the synthesis of LiFePO4 for battery

NASA Astrophysics Data System (ADS)

Tith, Rany; Dutta, Jaydeep; Jung, Kichang; Martinez-Morales, Alfredo A.

2017-05-01

LiFePO4 is a highly researched cathode material that serves as an alternative material for traditional commercial lithiumion batteries such as LiCoO2. Currently, there are a number of different methods to synthesize LiFePO4 including: hydrothermal, solid state, spray pyrolysis, and coprecipitation. Our proposed method has the potential to provide an ecologically friendly and economically competitive way to synthesize LiFePO4 by utilizing ionic liquid and water, as a composite synthesis medium. The addition of water to ionic liquid can be beneficial as it can act as a mineralizer to bring insoluble precursors to form LiFePO4 seed crystals. Furthermore, this method provides the possibility of recycling the ionic liquid for repeated synthesis processes. In this work, we study the effects of ionic liquid to water ratio on the crystallinity and morphology of the synthesized material. Our group was able to conclude a reaction medium utilizing a ratio of equal parts of 1-ethyl-3-methyl imidazolium trifluoromethane sulfonate (EMIM Otf) and water, or a slightly favored ionic liquid ratio, increases the efficacy of the synthesis route. Crystallinity and purity was determined by X-ray diffraction (XRD), scanning electron microscopy (SEM) was used to determine morphology and crystal sizes, and energy dispersion spectroscopy (EDX) was used for elemental analysis.

NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors

PubMed Central

2015-01-01

Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors. PMID:25973552

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Fluorinated ionic liquids for protein drug delivery systems: Investigating their impact on the structure and function of lysozyme.

PubMed

Alves, Márcia; Vieira, Nicole S M; Rebelo, Luís Paulo N; Araújo, João M M; Pereiro, Ana B; Archer, Margarida

2017-06-30

Since the approval of recombinant human insulin by FDA in 1982, more than 200 proteins are currently available for pharmaceutical use to treat a wide range of diseases. However, innovation is still required to develop effective approaches for drug delivery. Our aim is to investigate the potential use of fluorinated ionic liquids (FILs) as drug delivery systems (DDS) for therapeutic proteins. Some initial parameters need to be assessed before further studies can proceed. This work evaluates the impact of FILs on the stability, function, structure and aggregation state of lysozyme. Different techniques were used for this purpose, which included differential scanning fluorimetry (DSF), spectrophotometric assays, circular dichroism (CD), dynamic light scattering (DLS), and scanning and transmission electron microscopy (SEM/TEM). Ionic liquids composed of cholinium-, imidazolium- or pyridinium- derivatives were combined with different anions and analysed at different concentrations in aqueous solutions (below and above the critical aggregation concentration, CAC). The results herein presented show that the addition of ionic liquids had no significant effect on the stability and hydrolytic activity of lysozyme. Moreover, a distinct behaviour was observed in DLS experiments for non-surfactant and surfactant ionic liquids, with the latter encapsulating the protein at concentrations above the CAC. These results encourage us to further study ionic liquids as promising tools for DDS of protein drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Ion diffusion may introduce spurious current sources in current-source density (CSD) analysis.

PubMed

Halnes, Geir; Mäki-Marttunen, Tuomo; Pettersen, Klas H; Andreassen, Ole A; Einevoll, Gaute T

2017-07-01

Current-source density (CSD) analysis is a well-established method for analyzing recorded local field potentials (LFPs), that is, the low-frequency part of extracellular potentials. Standard CSD theory is based on the assumption that all extracellular currents are purely ohmic, and thus neglects the possible impact from ionic diffusion on recorded potentials. However, it has previously been shown that in physiological conditions with large ion-concentration gradients, diffusive currents can evoke slow shifts in extracellular potentials. Using computer simulations, we here show that diffusion-evoked potential shifts can introduce errors in standard CSD analysis, and can lead to prediction of spurious current sources. Further, we here show that the diffusion-evoked prediction errors can be removed by using an improved CSD estimator which accounts for concentration-dependent effects. NEW & NOTEWORTHY Standard CSD analysis does not account for ionic diffusion. Using biophysically realistic computer simulations, we show that unaccounted-for diffusive currents can lead to the prediction of spurious current sources. This finding may be of strong interest for in vivo electrophysiologists doing extracellular recordings in general, and CSD analysis in particular. Copyright © 2017 the American Physiological Society.

Lignin triggers irreversible cellulase loss during pretreated lignocellulosic biomass saccharification.

PubMed

Gao, Dahai; Haarmeyer, Carolyn; Balan, Venkatesh; Whitehead, Timothy A; Dale, Bruce E; Chundawat, Shishir Ps

2014-01-01

Non-productive binding of enzymes to lignin is thought to impede the saccharification efficiency of pretreated lignocellulosic biomass to fermentable sugars. Due to a lack of suitable analytical techniques that track binding of individual enzymes within complex protein mixtures and the difficulty in distinguishing the contribution of productive (binding to specific glycans) versus non-productive (binding to lignin) binding of cellulases to lignocellulose, there is currently a poor understanding of individual enzyme adsorption to lignin during the time course of pretreated biomass saccharification. In this study, we have utilized an FPLC (fast protein liquid chromatography)-based methodology to quantify free Trichoderma reesei cellulases (namely CBH I, CBH II, and EG I) concentration within a complex hydrolyzate mixture during the varying time course of biomass saccharification. Three pretreated corn stover (CS) samples were included in this study: Ammonia Fiber Expansion(a) (AFEX™-CS), dilute acid (DA-CS), and ionic liquid (IL-CS) pretreatments. The relative fraction of bound individual cellulases varied depending not only on the pretreated biomass type (and lignin abundance) but also on the type of cellulase. Acid pretreated biomass had the highest levels of non-recoverable cellulases, while ionic liquid pretreated biomass had the highest overall cellulase recovery. CBH II has the lowest thermal stability among the three T. reesei cellulases tested. By preparing recombinant family 1 carbohydrate binding module (CBM) fusion proteins, we have shown that family 1 CBMs are highly implicated in the non-productive binding of full-length T. reesei cellulases to lignin. Our findings aid in further understanding the complex mechanisms of non-productive binding of cellulases to pretreated lignocellulosic biomass. Developing optimized pretreatment processes with reduced or modified lignin content to minimize non-productive enzyme binding or engineering pretreatment-specific, low-lignin binding cellulases will improve enzyme specific activity, facilitate enzyme recycling, and thereby permit production of cheaper biofuels.

Non-synaptic ion channels in insects--basic properties of currents and their modulation in neurons and skeletal muscles.

PubMed

Wicher, D; Walther, C; Wicher, C

2001-08-01

Insects are favoured objects for studying information processing in restricted neuronal networks, e.g. motor pattern generation or sensory perception. The analysis of the underlying processes requires knowledge of the electrical properties of the cells involved. These properties are determined by the expression pattern of ionic channels and by the regulation of their function, e.g. by neuromodulators. We here review the presently available knowledge on insect non-synaptic ion channels and ionic currents in neurons and skeletal muscles. The first part of this article covers genetic and structural informations, the localization of channels, their electrophysiological and pharmacological properties, and known effects of second messengers and modulators such as neuropeptides or biogenic amines. In a second part we describe in detail modulation of ionic currents in three particularly well investigated preparations, i.e. Drosophila photoreceptor, cockroach DUM (dorsal unpaired median) neuron and locust jumping muscle. Ion channel structures are almost exclusively known for the fruitfly Drosophila, and most of the information on their function has also been obtained in this animal, mainly based on mutational analysis and investigation of heterologously expressed channels. Now the entire genome of Drosophila has been sequenced, it seems almost completely known which types of channel genes--and how many of them--exist in this animal. There is much knowledge of the various types of channels formed by 6-transmembrane--spanning segments (6TM channels) including those where four 6TM domains are joined within one large protein (e.g. classical Na+ channel). In comparison, two TM channels and 4TM (or tandem) channels so far have hardly been explored. There are, however, various well characterized ionic conductances, e.g. for Ca2+, Cl- or K+, in other insect preparations for which the channels are not yet known. In some of the larger insects, i.e. bee, cockroach, locust and moth, rather detailed information has been established on the role of ionic currents in certain physiological or behavioural contexts. On the whole, however, knowledge of non-synaptic ion channels in such insects is still fragmentary. Modulation of ion currents usually involves activation of more or less elaborate signal transduction cascades. The three detailed examples for modulation presented in the second part indicate, amongst other things, that one type of modulator usually leads to concerted changes of several ion currents and that the effects of different modulators in one type of cell may overlap. Modulators participate in the adaptive changes of the various cells responsible for different physiological or behavioural states. Further study of their effects on the single cell level should help to understand how small sets of cells cooperate in order to produce the appropriate output.

Entrainment Coefficient and Effective Mass for Conduction Neutrons in Neutron Star Crust:. Macroscopic Treatment

NASA Astrophysics Data System (ADS)

Carter, Brandon; Chamel, Nicolas; Haensel, Pawel

Phenomena such as pulsar frequency glitches are believed to be attributable to differential rotation of a current of "free" superfluid neutrons at densities above the "drip" threshold in the ionic crust of a neutron star. Such relative flow is shown to be locally describable by adaption of a canonical two-fluid treatment that emphasizes the role of the momentum covectors constructed by differentiation of action with respect to the currents, with allowance for stratification whereby the ionic number current may be conserved even when the ionic charge number Z is altered by beta processes. It is demonstrated that the gauge freedom to make different choices of the chemical basis determining which neutrons are counted as "free" does not affect their "superfluid" momentum covector, which must locally have the form of a gradient (though it does affect the "normal" momentum covector characterizing the protons and those neutrons that are considered to be "confined" in the nuclei). It is shown how the effect of "entrainment" (whereby the momentum directions deviate from those of the currents) is controlled by the (gauge-independent) mobility coefficient {K}, estimated in recent microscopical quantum mechanical investigations, which suggest that the corresponding (gauge-dependent) "effective mass" m⋆ of the free neutrons can become very large in some layers. The relation between this treatment of the crust layers and related work (using different definitions of "effective mass") intended for the deeper core layers is discussed.

Action Potential Energy Efficiency Varies Among Neuron Types in Vertebrates and Invertebrates

PubMed Central

Sengupta, Biswa; Stemmler, Martin; Laughlin, Simon B.; Niven, Jeremy E.

2010-01-01

The initiation and propagation of action potentials (APs) places high demands on the energetic resources of neural tissue. Each AP forces ATP-driven ion pumps to work harder to restore the ionic concentration gradients, thus consuming more energy. Here, we ask whether the ionic currents underlying the AP can be predicted theoretically from the principle of minimum energy consumption. A long-held supposition that APs are energetically wasteful, based on theoretical analysis of the squid giant axon AP, has recently been overturned by studies that measured the currents contributing to the AP in several mammalian neurons. In the single compartment models studied here, AP energy consumption varies greatly among vertebrate and invertebrate neurons, with several mammalian neuron models using close to the capacitive minimum of energy needed. Strikingly, energy consumption can increase by more than ten-fold simply by changing the overlap of the Na+ and K+ currents during the AP without changing the APs shape. As a consequence, the height and width of the AP are poor predictors of energy consumption. In the Hodgkin–Huxley model of the squid axon, optimizing the kinetics or number of Na+ and K+ channels can whittle down the number of ATP molecules needed for each AP by a factor of four. In contrast to the squid AP, the temporal profile of the currents underlying APs of some mammalian neurons are nearly perfectly matched to the optimized properties of ionic conductances so as to minimize the ATP cost. PMID:20617202

Electrochemical investigations of ionic liquids with vinylene carbonate for applications in rechargeable lithium ion batteries

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

Sun, Xiao-Guang; Dai, Sheng

2010-01-01

Ionic liquids based on methylpropylpyrrolidinium (MPPY) and methylpropylpiperidinium (MPPI) cations and bis(trifluoromethanesulfionyl)imide (TFSI) anion have been synthesized and characterized by thermal analysis, cyclic voltammetry, impedance spectroscopy as well as gavanostatic charge/discharge tests. 10 wt% of vinylene carbonate (VC) was added to the electrolytes of 0.5 M LiTFSI/MPPY.TFSI and 0.5 M LiTFSI/MPPI.TFSI, which were evaluated in Li || natural graphite (NG) half cells at 25 oC and 50 oC under different current densities. At 25 oC, due to their intrinsic high viscosities, the charge/discharge capacities under the current density of 80 A cm-2 were much lower than those under the currentmore » density of 40 A cm-2. At 50 oC, with reduced viscosities, the charge/discharge capacities under both current densities were almost indistinguishable, which were also close to the typical values obtained using conventional carbonate electrolytes. In addition, the discharge capacities of the half cells were very stable with cycling, due to the effective formation of solid electrolyte interphase (SEI) on the graphite electrode. On the contrary, the charge/discharge capacities of the Li || LiCoO2 cells using both ionic liquid electrolytes under the current density of 40 A cm-2 decreased continually with cycling, which were primarily due to the low oxidative stability of VC on the surface of LiCoO2.« less

Action potential energy efficiency varies among neuron types in vertebrates and invertebrates.

PubMed

Sengupta, Biswa; Stemmler, Martin; Laughlin, Simon B; Niven, Jeremy E

2010-07-01

The initiation and propagation of action potentials (APs) places high demands on the energetic resources of neural tissue. Each AP forces ATP-driven ion pumps to work harder to restore the ionic concentration gradients, thus consuming more energy. Here, we ask whether the ionic currents underlying the AP can be predicted theoretically from the principle of minimum energy consumption. A long-held supposition that APs are energetically wasteful, based on theoretical analysis of the squid giant axon AP, has recently been overturned by studies that measured the currents contributing to the AP in several mammalian neurons. In the single compartment models studied here, AP energy consumption varies greatly among vertebrate and invertebrate neurons, with several mammalian neuron models using close to the capacitive minimum of energy needed. Strikingly, energy consumption can increase by more than ten-fold simply by changing the overlap of the Na(+) and K(+) currents during the AP without changing the APs shape. As a consequence, the height and width of the AP are poor predictors of energy consumption. In the Hodgkin-Huxley model of the squid axon, optimizing the kinetics or number of Na(+) and K(+) channels can whittle down the number of ATP molecules needed for each AP by a factor of four. In contrast to the squid AP, the temporal profile of the currents underlying APs of some mammalian neurons are nearly perfectly matched to the optimized properties of ionic conductances so as to minimize the ATP cost.

Competitive adsorption from mixed hen egg-white lysozyme/surfactant solutions at the air-water interface studied by tensiometry, ellipsometry, and surface dilational rheology.

PubMed

Alahverdjieva, V S; Grigoriev, D O; Fainerman, V B; Aksenenko, E V; Miller, R; Möhwald, H

2008-02-21

The competitive adsorption at the air-water interface from mixed adsorption layers of hen egg-white lysozyme with a non-ionic surfactant (C10DMPO) was studied and compared to the mixture with an ionic surfactant (SDS) using bubble and drop shape analysis tensiometry, ellipsometry, and surface dilational rheology. The set of equilibrium and kinetic data of the mixed solutions is described by a thermodynamic model developed recently. The theoretical description of the mixed system is based on the model parameters for the individual components.

Ultrasensitive detection of protein translocated through toxin pores in droplet-interface bilayers

PubMed Central

Fischer, Audrey; Holden, Matthew A.; Pentelute, Brad L.; Collier, R. John

2011-01-01

Many bacterial toxins form proteinaceous pores that facilitate the translocation of soluble effector proteins across cellular membranes. With anthrax toxin this process may be monitored in real time by electrophysiology, where fluctuations in ionic current through these pores inserted in model membranes are used to infer the translocation of individual protein molecules. However, detecting the minute quantities of translocated proteins has been a challenge. Here, we describe use of the droplet-interface bilayer system to follow the movement of proteins across a model membrane separating two submicroliter aqueous droplets. We report the capture and subsequent direct detection of as few as 100 protein molecules that have translocated through anthrax toxin pores. The droplet-interface bilayer system offers new avenues of approach to the study of protein translocation. PMID:21949363

Reconstruction of electrocardiogram using ionic current models for heart muscles.

PubMed

Yamanaka, A; Okazaki, K; Urushibara, S; Kawato, M; Suzuki, R

1986-11-01

A digital computer model is presented for the simulation of the electrocardiogram during ventricular activation and repolarization (QRS-T waves). The part of the ventricular septum and the left ventricular free wall of the heart are represented by a two dimensional array of 730 homogeneous functional units. Ionic currents models are used to determine the spatial distribution of the electrical activities of these units at each instant of time during simulated cardiac cycle. In order to reconstruct the electrocardiogram, the model is expanded three-dimensionally with equipotential assumption along the third axis and then the surface potentials are calculated using solid angle method. Our digital computer model can be used to improve the understanding of the relationship between body surface potentials and intracellular electrical events.

Fabrications of insulator-protected nanometer-sized electrode gaps

NASA Astrophysics Data System (ADS)

Arima, Akihide; Tsutsui, Makusu; Morikawa, Takanori; Yokota, Kazumichi; Taniguchi, Masateru

2014-03-01

We developed SiO2-coated mechanically controllable break junctions for accurate tunneling current measurements in an ionic solution. By breaking the junction, we created dielectric-protected Au nanoprobes with nanometer separation. We demonstrated that the insulator protection was capable to suppress the ionic contribution to the charge transport through the electrode gap, thereby enabled reliable characterizations of liquid-mediated exponential decay of the tunneling conductance in an electrolyte solution. From this, we found distinct roles of charge points such as molecular dipoles and ion species on the tunneling decay constant, which was attributed to local structures of molecules and ions in the confined space between the sensing electrodes. The device described here would provide improved biomolecular sensing capability of tunneling current sensors.

CO2 capture by ionic liquids - an answer to anthropogenic CO2 emissions?

PubMed

Sanglard, Pauline; Vorlet, Olivier; Marti, Roger; Naef, Olivier; Vanoli, Ennio

2013-01-01

Ionic liquids (ILs) are efficient solvents for the selective removal of CO2 from flue gas. Conventional, offthe-shelf ILs are limited in use to physisorption, which restricts their absorption capacity. After adding a chemical functionality like amines or alcohols, absorption of CO2 occurs mainly by chemisorption. This greatly enhances CO2 absorption and makes ILs suitable for potential industrial applications. By carefully choosing the anion and the cation of the IL, equimolar absorption of CO2 is possible. This paper reviews the current state of the art of CO2 capture by ILs and presents the current research in this field performed at the ChemTech Institute of the Ecole d'Ingénieurs et d'Architectes de Fribourg.

An ionic liquid-gated polymer thin film transistor with exceptionally low "on" resistance

NASA Astrophysics Data System (ADS)

Algarni, Saud A.; Althagafi, Talal M.; Smith, Patrick J.; Grell, Martin

2014-05-01

We report the ionic liquid (IL) gating of a solution processed semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT). IL gating relies on the poor solubility of PBTTT, which requires hot chlorinated benzenes for solution processing. PBTTT, thus, resists dissolution even in IL, which otherwise rapidly dissolves semiconducting polymers. The resulting organic thin film transistors (OTFTs) display low threshold, very high carrier mobility (>3 cm2/Vs), and deliver high currents (in the order of 1 mA) at low operational voltages. Such OTFTs are interesting both practically, for the addressing of current-driven devices (e.g., organic LEDs), and for the study of charge transport in semiconducting polymers at very high carrier density.

Cellular defibrillation: interaction of micro-scale electric fields with voltage-gated ion channels.

PubMed

Kargol, Armin; Malkinski, Leszek; Eskandari, Rahmatollah; Carter, Maya; Livingston, Daniel

2015-09-01

We study the effect of micro-scale electric fields on voltage-gated ion channels in mammalian cell membranes. Such micro- and nano-scale electric fields mimic the effects of multiferroic nanoparticles that were recently proposed [1] as a novel way of controlling the function of voltage-sensing biomolecules such as ion channels. This article describes experimental procedures and initial results that reveal the effect of the electric field, in close proximity of cells, on the ion transport through voltage-gated ion channels. We present two configurations of the whole-cell patch-clamping apparatus that were used to detect the effect of external stimulation on ionic currents and discuss preliminary results that indicate modulation of the ionic currents consistent with the applied stimulus.

A hybrid nanosensor for TNT vapor detection.

PubMed

Díaz Aguilar, Alvaro; Forzani, Erica S; Leright, Mathew; Tsow, Francis; Cagan, Avi; Iglesias, Rodrigo A; Nagahara, Larry A; Amlani, Islamshah; Tsui, Raymond; Tao, N J

2010-02-10

Real-time detection of trace chemicals, such as explosives, in a complex environment containing various interferents has been a difficult challenge. We describe here a hybrid nanosensor based on the electrochemical reduction of TNT and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts-per-trillion level TNT in the presence of various interferents within a few minutes.

Ionic electroactive polymer actuators as active microfluidic mixers

DOE PAGES

Meis, Catherine; Montazami, Reza; Hashemi, Nastaran

2015-11-06

On-chip sample processing is integral to the continued development of lab-on-a-chip devices for various applications. An active microfluidic mixer prototype is proposed using ionic electroactive polymer actuators (IEAPAs) as artificial cilia. A proof-of-concept experiment was performed in which the actuators were shown to produce localized flow pattern disruptions in the laminar flow regime. Suggestions for further engineering and optimization of a scaled-down, complete device are provided. Furthermore, the device in its current state of development necessitates further engineering, the use of IEAPAs addresses issues currently associated with the use of electromechanical actuators as active microfluidic mixers and may prove tomore » be a useful alternative to other similar materials.« less

Very deep spectroscopy of the bright Saturn nebula NGC 7009 - II. Analysis of the rich optical recombination spectrum

NASA Astrophysics Data System (ADS)

Fang, X.; Liu, X.-W.

2013-03-01

In Paper I, we presented a deep, long-slit spectrum of the bright Saturn nebula NGC 7009. Numerous permitted lines emitted by the C+, N+, O+ and Ne+ ions were detected. Gaussian profile fitting to the spectrum yielded more than 1000 lines, the majority of which are optical recombination lines (ORLs) of heavy-element ions. In the current paper, we present a critical analysis of the rich optical recombination spectrum of NGC 7009, in the context of the bi-abundance nebular model proposed by Liu et al. Transitions from individual multiplets are checked carefully for potential blended lines. The observed relative intensities are compared with the theoretical predictions based on high-quality effective recombination coefficients, now available for the recombination line spectrum of a number of heavy-element ions. The possibility of plasma diagnostics using the ORLs of various heavy-element ions is discussed in detail. The line ratios that can be used to determine electron temperature are presented for each ion, although there is still a lack of adequate atomic data and some of the lines are still not detected in the spectrum of NGC 7009 due to weakness and/or line blending. Plasma diagnostics based on the N II and O II recombination spectra both yield electron temperatures close to 1000 K, which is lower than those derived from the collisionally excited line (CEL) ratios (e.g. the [O III] and [N II] nebular-to-auroral line ratios; see Paper I for details) by nearly one order of magnitude. The very low temperatures yielded by the O II and N II ORLs indicate that they originate from very cold regions. The C2+/H+, N2+/H+, O2+/H+ and Ne2+/H+ ionic abundance ratios derived from ORLs are consistently higher, by about a factor of 5, than the corresponding values derived from CELs. In calculating the ORL ionic abundance ratios, we have used the newly available high-quality effective recombination coefficients, and adopted an electron temperature of ˜1000 K, as given by the ORL diagnostics and as a consequence presumably representing the physical conditions prevailing in the regions where the heavy-element ORLs arise. Measurements of the ultraviolet (UV) and infrared (IR) CELs from the literature are used to calculate CEL ionic abundance ratios when optical data are not available for the ionic species. A comparison of results of plasma diagnostics and abundance determinations for NGC 7009 points to the existence of `cold', metal-rich (i.e. H-deficient) inclusions embedded in the hot, diffuse ionized gas, first postulated by Liu et al. At electron temperatures yielded by the N II and O II ORLs, the predicted relative intensities of ORLs agree well with the observed values, indicating that the current quantum calculations of the recombination spectra of those two ionic species well represent the recombination processes under nebular conditions. Deviations from the LS coupling, noticed in an earlier quantitative spectroscopy by Liu et al. for the same object, are again confirmed, especially for recombination lines of the 4f-3d transition array. For N II, as well as for O II, the ionic abundances derived from different J-resolved transitions within a multiplet, or from the transitions belonging to different multiplets, agree with each other. This is another evidence that the new effective recombination coefficients are reliable. New calculations of the effective recombination coefficients for the Ne II lines at nebular temperatures and densities are needed.

Battery Structures, self-organizing structures, and related methods

DOEpatents

Chiang, Yet-Ming; Moorehead, William Douglas

2013-11-12

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

Battery structures, self-organizing structures and related methods

DOEpatents

Chiang, Yet-Ming [Framingham, MA; Moorehead, William Douglas [Virginia Beach, VA

2012-06-26

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

Fluidic nanotubes and devices

DOEpatents

Yang, Peidong [Berkeley, CA; He, Rongrui [El Cerrito, CA; Goldberger, Joshua [Berkeley, CA; Fan, Rong [El Cerrito, CA; Wu, Yiying [Albany, CA; Li, Deyu [Albany, CA; Majumdar, Arun [Orinda, CA

2008-04-08

Fluidic nanotube devices are described in which a hydrophilic, non-carbon nanotube, has its ends fluidly coupled to reservoirs. Source and drain contacts are connected to opposing ends of the nanotube, or within each reservoir near the opening of the nanotube. The passage of molecular species can be sensed by measuring current flow (source-drain, ionic, or combination). The tube interior can be functionalized by joining binding molecules so that different molecular species can be sensed by detecting current changes. The nanotube may be a semiconductor, wherein a tubular transistor is formed. A gate electrode can be attached between source and drain to control current flow and ionic flow. By way of example an electrophoretic array embodiment is described, integrating MEMs switches. A variety of applications are described, such as: nanopores, nanocapillary devices, nanoelectrophoretic, DNA sequence detectors, immunosensors, thermoelectric devices, photonic devices, nanoscale fluidic bioseparators, imaging devices, and so forth.

Fluidic nanotubes and devices

DOEpatents

Yang, Peidong; He, Rongrui; Goldberger, Joshua; Fan, Rong; Wu, Yiying; Li, Deyu; Majumdar, Arun

2010-01-10

Fluidic nanotube devices are described in which a hydrophilic, non-carbon nanotube, has its ends fluidly coupled to reservoirs. Source and drain contacts are connected to opposing ends of the nanotube, or within each reservoir near the opening of the nanotube. The passage of molecular species can be sensed by measuring current flow (source-drain, ionic, or combination). The tube interior can be functionalized by joining binding molecules so that different molecular species can be sensed by detecting current changes. The nanotube may be a semiconductor, wherein a tubular transistor is formed. A gate electrode can be attached between source and drain to control current flow and ionic flow. By way of example an electrophoretic array embodiment is described, integrating MEMs switches. A variety of applications are described, such as: nanopores, nanocapillary devices, nanoelectrophoretic, DNA sequence detectors, immunosensors, thermoelectric devices, photonic devices, nanoscale fluidic bioseparators, imaging devices, and so forth.

Battery structures, self-organizing structures and related methods

DOEpatents

Chiang, Yet Ming [Framingham, MA; Moorehead, William Douglas [Virginia Beach, VA; Gozdz, Antoni S [Marlborough, MA; Holman, Richard K [Belmont, MA; Loxley, Andrew [Somerville, MA; Riley, Jr., Gilbert N.; Viola, Michael S [Burlington, MA

2009-08-25

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

Battery structures, self-organizing structures and related methods

DOEpatents

Chiang, Yet-Ming [Framingham, MA; Moorehead, William D [Virginia Beach, VA; Gozdz, Antoni S [Marlborough, MA; Holman, Richard K [Belmont, MA; Loxley, Andrew L [Roslindale, MA; Riley, Jr., Gilbert N.; Viola, Michael S [Burlington, MA

2012-05-01

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

Battery structures, self-organizing structures and related methods

DOEpatents

Chiang, Yet-Ming [Framingham, MA; Moorehead, William D [Virginia Beach, VA; Gozdz, Antoni S [Marlborough, MA; Holman, Richard K [Belmont, MA; Loxley, Andrew L [Roslindale, MA; Riley, Jr., Gilbert N.; Viola, Michael S [Burlington, MA

2011-08-02

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

An efficient technique for the numerical solution of the bidomain equations.

PubMed

Whiteley, Jonathan P

2008-08-01

Computing the numerical solution of the bidomain equations is widely accepted to be a significant computational challenge. In this study we extend a previously published semi-implicit numerical scheme with good stability properties that has been used to solve the bidomain equations (Whiteley, J.P. IEEE Trans. Biomed. Eng. 53:2139-2147, 2006). A new, efficient numerical scheme is developed which utilizes the observation that the only component of the ionic current that must be calculated on a fine spatial mesh and updated frequently is the fast sodium current. Other components of the ionic current may be calculated on a coarser mesh and updated less frequently, and then interpolated onto the finer mesh. Use of this technique to calculate the transmembrane potential and extracellular potential induces very little error in the solution. For the simulations presented in this study an increase in computational efficiency of over two orders of magnitude over standard numerical techniques is obtained.

Coherent structure in solar wind C{sup 6+}/C{sup 4+} ionic composition data during the quiet-sun conditions of 2008

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

Edmondson, J. K.; Lepri, S. T.; Zurbuchen, T. H.

2013-11-20

This analysis offers evidence of characteristic scale sizes in solar wind charge state data measured in situ for 13 quiet-Sun Carrington rotations in 2008. Using a previously established novel methodology, we analyze the wavelet power spectrum of the charge state ratio C{sup 6+}/C{sup 4+} measured in situ by ACE/SWICS for 2 hr and 12 minute cadence. We construct a statistical significance level in the wavelet power spectrum to quantify the interference effects arising from filling missing data in the time series, allowing extraction of significant power from the measured data to a resolution of 24 minutes. We analyze each waveletmore » power spectrum for transient coherency and global periodicities resulting from the superposition of repeating coherent structures. From the significant wavelet power spectra, we find evidence for a general upper limit on individual transient coherency of ∼10 days. We find evidence for a set of global periodicities between 4-5 hr and 35-45 days. We find evidence for the distribution of individual transient coherency scales consisting of two distinct populations. Below the ∼2 day timescale, the distribution is reasonably approximated by an inverse power law, whereas for scales ≳2 days, the distribution levels off, showing discrete peaks at common coherency scales. In addition, by organizing the transient coherency scale distributions by wind type, we find that these larger, common coherency scales are more prevalent and well defined in coronal hole wind. Finally, we discuss the implications of our results for current theories of solar wind generation and describe future work for determining the relationship between the coherent structures in our ionic composition data and the structure of the coronal magnetic field.« less

[Ionic mechanisms of depolarization responses induced by glutamate application to nerve cells of Helix pomatia].

PubMed

Gerasimov, V D

1982-01-01

The reversal potentials for transmembrane ionic currents induced by glutamate were measured in different D-neurons of the snail Helix pomatia. The first group of neurons had a mean reversal potential--10.6 +/- 1.2 mV and the second one--40.0 +/- 0.6 mV. Under normal conditions glutamate evoked spike discharges in the first group of neurons but not in the second one. At higher concentrations of glutamate the amplitude of D-responses in the latter group increased only to a certain level, not reaching the critical level for cell firing. Decrease in external Cl concentration led to a shift of their reversal potential in depolarizing direction. Ionic mechanisms of depolarizing responses induced by glutamate in these groups of neurons are discussed.

Differential roles of two delayed rectifier potassium currents in regulation of ventricular action potential duration and arrhythmia susceptibility.

PubMed

Devenyi, Ryan A; Ortega, Francis A; Groenendaal, Willemijn; Krogh-Madsen, Trine; Christini, David J; Sobie, Eric A

2017-04-01

Arrhythmias result from disruptions to cardiac electrical activity, although the factors that control cellular action potentials are incompletely understood. We combined mathematical modelling with experiments in heart cells from guinea pigs to determine how cellular electrical activity is regulated. A mismatch between modelling predictions and the experimental results allowed us to construct an improved, more predictive mathematical model. The balance between two particular potassium currents dictates how heart cells respond to perturbations and their susceptibility to arrhythmias. Imbalances of ionic currents can destabilize the cardiac action potential and potentially trigger lethal cardiac arrhythmias. In the present study, we combined mathematical modelling with information-rich dynamic clamp experiments to determine the regulation of action potential morphology in guinea pig ventricular myocytes. Parameter sensitivity analysis was used to predict how changes in ionic currents alter action potential duration, and these were tested experimentally using dynamic clamp, a technique that allows for multiple perturbations to be tested in each cell. Surprisingly, we found that a leading mathematical model, developed with traditional approaches, systematically underestimated experimental responses to dynamic clamp perturbations. We then re-parameterized the model using a genetic algorithm, which allowed us to estimate ionic current levels in each of the cells studied. This unbiased model adjustment consistently predicted an increase in the rapid delayed rectifier K + current and a drastic decrease in the slow delayed rectifier K + current, and this prediction was validated experimentally. Subsequent simulations with the adjusted model generated the clinically relevant prediction that the slow delayed rectifier is better able to stabilize the action potential and suppress pro-arrhythmic events than the rapid delayed rectifier. In summary, iterative coupling of simulations and experiments enabled novel insight into how the balance between cardiac K + currents influences ventricular arrhythmia susceptibility. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

Reconstruction of ionic currents in a molluscan photoreceptor.

PubMed Central

Sakakibara, M.; Ikeno, H.; Usui, S.; Collin, C.; Alkon, D. L.

1993-01-01

Two-microelectrode voltage-clamp measurements were made to determine the kinetics and voltage dependence of ionic currents across the soma membrane of the Hermissenda type B photoreceptor. The voltage-dependent outward potassium currents, IA and ICa(2+)-K+, the inward voltage-dependent calcium current, ICa2+ and the light-induced current, IIgt, were then described with Hodgkin-Huxley-type equations. The fast-activating and inactivating potassium current, IA, was described by the equation; IA(t) = gA(max)(ma infinity[1-exp(-t/tau ma)])3 x (ha infinity [1-exp(-t/tau ha)] + exp(-t/tau ha)) (Vm-EK), where the parameters ma infinity, ha infinity, tau ma, and tau ha are functions of membrane potential, Vm, and ma infinity and ha infinity are steady-state activation and inactivation parameters. Similarly, the calcium-dependent outward potassium current, ICa(2+)-K+, was described by the equation, ICa(2+)-K+ (t) = gc(max)(mc infinity(VC)(1-exp[-t/tau mc (VC)]))pc (hc infinity(VC) [1-exp(-t/tau hc)] + exp(-t/tau hc(VC)])pc(VC-EK). In high external potassium, ICa(2+)-K+ could be measured in approximate isolation from other currents as a voltage-dependent inward tail current following a depolarizing command pulse from a holding potential of -60 mV. A voltage-dependent inward calcium current across the type B soma membrane, ICa2+, activated rapidly, showed little inactivation, and was described by the equation: ICa2+ = gCa(max) [1 + exp](-Vm-5)/7]-1 (Vm-ECa), where gCa(max) was 0.5 microS. The light-induced current with both fast and slow phases was described by: IIgt(t) = IIgt1 + IIgt2 + IIgt3, IIgti = gIgti [1-exp(- ton/tau mi)] exp(-ton/tau hi)(Vm-EIgti) (i = 1, 2). For i = 3, /Igt(t) = gigt3m33h3(Vm - Eigt3)exp(-ton/Ton) x exp(-tfoff/t Off). Based on these reconstructions of ionic currents, learning-induced enhancement of the long lasting depolarization (LLD) of the photoreceptor'slight response was shown to arise from progressive inactivation of /A, lca2+ -K+, and lCa2+. PMID:8369456

Biomimetic heterogeneous multiple ion channels: a honeycomb structure composite film generated by breath figures

NASA Astrophysics Data System (ADS)

Han, Keyu; Heng, Liping; Wen, Liping; Jiang, Lei

2016-06-01

We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields.We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields. Electronic supplementary information (ESI) available: Pore size distribution histograms of the AAO substrates; SEM images of the side view of pure AAO membranes and top view of the flat PI/AAO composite film; the current-time curves of the flat composite film; the current-voltage characteristics curves of pure AAO nanochannels with different mean pore diameters; CA of the two surfaces of the composite PI/AAO film, the structural formula of the polymer polyimide resin (PI), and solid surface zeta potential. See DOI: 10.1039/c6nr02506d

Oscillatory nonohomic current drive for maintaining a plasma current

DOEpatents

Fisch, N.J.

1984-01-01

Apparatus and methods are described for maintaining a plasma current with an oscillatory nonohmic current drive. Each cycle of operation has a generation period in which current driving energy is applied to the plasma, and a relaxation period in which current driving energy is removed. Plasma parameters, such as plasma temperature or plasma average ionic charge state, are modified during the generation period so as to oscillate plasma resistivity in synchronism with the application of current driving energy. The invention improves overall current drive efficiencies.

Oscillatory nonhmic current drive for maintaining a plasma current

DOEpatents

Fisch, Nathaniel J.

1986-01-01

Apparatus and method of the invention maintain a plasma current with an oscillatory nonohmic current drive. Each cycle of operation has a generation period in which current driving energy is applied to the plasma, and a relaxation period in which current driving energy is removed. Plasma parameters, such as plasma temperature or plasma average ionic charge state, are modified during the generation period so as to oscillate plasma resistivity in synchronism with the application of current driving energy. The invention improves overall current drive efficiencies.

Electrodialytic in-line preconcentration for ionic solute analysis.

PubMed

Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

2018-04-01

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

Proximity and touch sensing using deformable ionic conductors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Madden, John D. W.; Dobashi, Yuta; Sarwar, Mirza S.; Preston, Eden C.; Wyss, Justin K. M.; Woehling, Vincent; Nguyen, Tran-Minh-Giao; Plesse, Cedric; Vidal, Frédéric; Naficy, Sina; Spinks, Geoffrey M.

2017-04-01

There is increasing interest in creating bendable and stretchable electronic interfaces that can be worn or applied to virtually any surface. The electroactive polymer community is well placed to add value by incorporating sensors and actuators. Recent work has demonstrated transparent dielectric elastomer actuation as well as pressure, stretch or touch sensing. Here we present two alternative forms of sensing. The first uses ionically conductive and stretchable gels as electrodes in capacitive sensors that detect finger proximity. In this case the finger acts as a third electrode, reducing capacitance between the two gel electrodes as it approaches, which can be detected even during bending and stretching. Very light finger touch is readily detected even during deformation of the substrate. Lateral resolution is achieved by creating a sensor array. In the second approach, electrodes placed beneath a salt containing gel are able to detect ion currents generated by the deformation of the gel. In this approach, applied pressure results in ion currents that create a potential difference around the point of contact, leading to a voltage and current in the electrodes without any need for input electrical energy. The mechanism may be related to effects seen in ionomeric polymer metal composites (IPMCs), but with the response in plane rather than through the thickness of the film. Ultimately, these ionically conductive materials that can also be transparent and actuate, have the potential to be used in wearable devices.

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

PubMed Central

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-01-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

NASA Astrophysics Data System (ADS)

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-09-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

Structural Integrity of Proteins under Applied Bias during Solid-State Nanopore Translocation

NASA Astrophysics Data System (ADS)

Hasan, Mohammad R.; Khanzada, Raja Raheel; Mahmood, Mohammed A. I.; Ashfaq, Adnan; Iqbal, Samir M.

2015-03-01

The translocation behavior of proteins through solid-state nanopores can be used as a new way to detect and identify proteins. The ionic current through a nanopore that flows under applied bias gets perturbed when a biomolecule traverses the Nanopore. It is important for a protein detection scheme to know of any changes in the three-dimensional structure of the molecule during the process. Here we report the data on structural integrity of protein during translocation through nanopore under different applied biases. Nanoscale Molecular Dynamic was used to establish a framework to study the changes in protein structures as these travelled across the nanopore. The analysis revealed the contributions of structural changes of protein to its ionic current signature. As a model, thrombin protein crystalline structure was imported and positioned inside a 6 nm diameter pore in a 6 nm thick silicon nitride membrane. The protein was solvated in 1 M KCl at 295 K and the system was equilibrated for 20 ns to attain its minimum energy state. The simulation was performed at different electric fields from 0 to 1 kCal/(mol.Å.e). RMSD, radial distribution function, movement of the center of mass and velocity of the protein were calculated. The results showed linear increments in the velocity and perturbations in ionic current profile with increasing electric potential. Support Acknowledged from NSF through ECCS-1201878.

Beta-phenylethylamine inhibits K+ currents in neocortical neurons of the rat: a possible mechanism of beta-phenylethylamine-induced seizures.

PubMed

Kitamura, Taro; Munakata, Mitsutoshi; Haginoya, Kazuhiro; Tsuchiya, Shigeru; Iinuma, Kazuie

2008-08-01

beta-Phenylethylamine (beta-PEA), an endogenous amine synthesized in the brain, serves as a neuromodulator and is involved in the pathophysiology of various neurological disorders such as depression, schizophrenia, and attention-deficit hyperactivity disorder. beta-PEA fully exerts the physiological effects within the nanomolar concentration range via the trace amine receptors, but beta-PEA also causes convulsions at much higher concentrations via an as yet unknown mechanism. To investigate the electrophysiological mechanism by which beta-PEA induces convulsions, we examined the effect of beta-PEA on ionic currents passing through the cell membrane of dissociated rat cerebral cortical neurons, using a patch-clamp technique. The external application of beta-PEA suppressed ionic currents which continuously flowed when the membrane potential was held at -25 mV. The suppression was in a concentration-dependent manner and a half-maximal effective concentration was 540 muM. These currents suppressed by beta-PEA consisted of two K(+) currents: a time- and voltage-dependent K(+) current (M-current) and a leakage K(+) current. The suppression of the M-current reduces the efficacy of the current in limiting excessive neuronal firing, and the suppression of the leakage K(+) current can cause membrane depolarization and thus promote neuronal excitation. Reducing both of these currents in concert may produce neuronal seizing activity, which could conceivably underlie the convulsions induced by high-dose beta-PEA.

Large and persistent electrical currents enter the transected lamprey spinal cord.

PubMed Central

Borgens, R B; Jaffe, L F; Cohen, M J

1980-01-01

The electrical currents at the surface of the proximal portion of an isolated and transected lamprey spinal cord were measured with an extracellular vibrating probe. Soon after transection, currents of about 0.5 mA/cm2 enter the cut surface of the spinal cord. These currents fall to about a quarter of their initial value within an hour; within the next 2 days they gradually decline from about 100 microA/cm2 to about 4 microA/cm2; they then remain constant up to 6 days posttransection, when the measurements were ended. The pattern of current entry included substantial peaks opposite (and presumably into) the cut ends of giant axons. Response to changes in the ionic composition of the medium indicates that about half of the injury current consists of Na+, and that much of the rest may consist of Ca2+. The measured influx of ions, which adds up to several coulombs per cm2 in a few days, should radically alter the ionic composition of the terminal few millimeters of neural tissue. Thus it may be important in the degenerative and regenerative responses of neurons to axotomy. Images PMID:6928670

Ionic Current Measurements in the Squid Giant Axon Membrane

PubMed Central

Cole, Kenneth S.; Moore, John W.

1960-01-01

The concepts, experiments, and interpretations of ionic current measurements after a step change of the squid axon membrane potential require the potential to be constant for the duration and the membrane area measured. An experimental approach to this ideal has been developed. Electrometer, operational, and control amplifiers produce the step potential between internal micropipette and external potential electrodes within 40 microseconds and a few millivolts. With an internal current electrode effective resistance of 2 ohm cm.2, the membrane potential and current may be constant within a few millivolts and 10 per cent out to near the electrode ends. The maximum membrane current patterns of the best axons are several times larger but of the type described by Cole and analyzed by Hodgkin and Huxley when the change of potential is adequately controlled. The occasional obvious distortions are attributed to the marginal adequacy of potential control to be expected from the characteristics of the current electrodes and the axon. Improvements are expected only to increase stability and accuracy. No reason has been found either to question the qualitative characteristics of the early measurements or to so discredit the analyses made of them. PMID:13694548

Ionic current rectification in organic solutions with quartz nanopipettes.

PubMed

Yin, Xiaohong; Zhang, Shudong; Dong, Yitong; Liu, Shujuan; Gu, Jing; Chen, Ye; Zhang, Xin; Zhang, Xianhao; Shao, Yuanhua

2015-09-01

The study of behaviors of ionic current rectification (ICR) in organic solutions with quartz nanopipettes is reported. ICR can be observed even in organic solutions using quartz pipettes with diameters varied from several to dozens of nanometers, and the direction of ICR is quite different from the ICR observed in aqueous phase. The influences of pore size, electrolyte concentration, and surface charge on the ICR have been investigated carefully. Water in organic solutions affects the direction and extent of ICR significantly. Mechanisms about the formation of an electrical double layer (EDL) on silica in organic solutions with different amount of water have been proposed. An improved method, which can be employed to detect trace water in organic solutions, has been implemented based on Au ultramicroelectrodes with cathodic differential pulse stripping voltammetry.

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Ionic Liquid Directed Mesoporous Carbon Nanoflakes as an Effiencient Electrode material

NASA Astrophysics Data System (ADS)

Kong, Lirong; Chen, Wei

2015-12-01

Supercapacitors are considered to be the most promising approach to meet the pressing requirements for energy storage devices. The electrode materials for supercapacitors have close relationship with their electrochemical properties and thus become the key point to improve their energy storage efficiency. Herein, by using poly (vinylidene fluoride-co-hexafluoropropylene) and ionic liquid as the dual templates, polyacrylonitrile as the carbon precursor, a flake-like carbon material was prepared by a direct carbonization method. In this method, poly (vinylidene fluoride-co-hexafluoropropylene) worked as the separator for the formation of isolated carbon flakes while aggregated ionic liquid worked as the pore template. The obtained carbon flakes exhibited a specific capacitance of 170 F/g at 0.1 A/g, a high energy density of 12.2 Wh/kg and a high power density of 5 kW/kg at the current of 10 A/g. It also maintained a high capacitance retention capability with almost no declination after 500 charge-discharge cycles. The ionic liquid directed method developed here also provided a new idea for the preparation of hierarchically porous carbon nanomaterials.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

PubMed

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-17

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

NASA Astrophysics Data System (ADS)

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-01

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g-1 at a current density of 2 A g-1, when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg-1 and 41 Wh kg-1, respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

Visualization of TlBr ionic transport mechanism by the Accelerated Device Degradation technique

NASA Astrophysics Data System (ADS)

Datta, Amlan; Becla, Piotr; Motakef, Shariar

2015-06-01

Thallium Bromide (TlBr) is a promising gamma radiation semiconductor detector material. However, it is an ionic semiconductor and suffers from polarization. As a result, TlBr devices degrade rapidly at room temperature. Polarization is associated with the flow of ionic current in the crystal under electrical bias, leading to the accumulation of charged ions at the device's electrical contacts. We report a fast and reliable direct characterization technique to identify the effects of various growth and post-growth process modifications on the polarization process. The Accelerated Device Degradation (ADD) characterization technique allows direct observation of nucleation and propagation of ionic transport channels within the TlBr crystals under applied bias. These channels are observed to be initiated both directly under the electrode as well as away from it. The propagation direction is always towards the anode indicating that Br- is the mobile diffusing species within the defect channels. The effective migration energy of the Br- ions was calculated to be 0.33±0.03 eV, which is consistent with other theoretical and experimental results.

Polarization effect in the Ionic conductor TlBr

NASA Astrophysics Data System (ADS)

Rocha Leao, Cedric; Lordi, Vincenzo

2012-02-01

TlBr is an ionic crystal that in recent years has been standing out as one of the most promising materials for effective room temperature radiation detection. However, its exceptional performance invariably degrades after operation times that vary from hours to several weeks. This phenomenon, known as polarization, is assigned to the undesirable ionic current that sets in the crystal under an applied bias, leading to the accumulation of oppositely charged Tl+ and Br- ions at the electric contacts of the device. This charge build up induces a field that opposes the applied bias, impairing the collection of the photo-induced carriers. In this presentation, we use parameter free quantum mechanical simulations to discuss the possible origins of the polarization effect in TlBr, showing that ionic mobility in the intrinsic material is not enough to account for effects reported by several groups. We then discuss other possible causes for the degradation of biased TlBr and propose ways to prevent its occurrence, via careful co-doping as well as a judicious choice of the metal contacts to be employed.

Aluminium electrodeposition in chloroaluminate ionic liquid.

PubMed

Zhang, Lipeng; Wang, Enqi; Mu, Jiechen; Yu, Xianjin; Wang, Qiannan; Yang, Lina; Zhao, Zengdian

2014-08-01

An efficient microwave enhanced synthesis of ambient temperature chloroaluminate ionic liquid ([EMIM]Br) that preceeds reaction of 1-methylimidazolium with bromoethane in a closed vessel, was described in our work. The reaction time was drastically reduced as compared to the conventional methods. The electrochemical techniques of impedance spectroscopy, cyclic voltammetry and chronoamperometry were used to investigate the mechanism of Al electrodeposition from 2:1 (molar ratio) AlCl3/[EMIM]Br ionic liquid at room temperature. Results indicated that Al electrode- position from this ionic liqud was a quasi-reversible process, and the kinetic complications during the reaction was probably attributed to the electron transfer or mass transport cooperative controlled processes, instantaneous nucleation with diffusion-controlled growth was also investigated. Electrodepositon experiment was conducted using constant current density of 40 mA·cm(-2) for 20 minutes at room temperature and the qualitative analysis of the deposits were performed using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and energy dispersive spectroscope (EDS). The deposits obtained on copper cathode were dense and compact and most Al crystal shows granular structure spherical with high purity.

Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

NASA Astrophysics Data System (ADS)

Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

2011-03-01

The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

Characterization of the Electric Double Layer Formation Dynamics of a Metal/Ionic Liquid/Metal Structure.

PubMed

Schmidt, Elliot; Shi, Sha; Ruden, P Paul; Frisbie, C Daniel

2016-06-15

Although ionic liquids (ILs) have been used extensively in recent years as a high-capacitance "dielectric" in electric double layer transistors, the dynamics of the double layer formation have remained relatively unexplored. Better understanding of the dynamics and relaxation processes involved in electric double layer formation will guide device optimization, particularly with regard to switching speed. In this paper, we explore the dynamical characteristics of an IL in a metal/ionic liquid/metal (M/IL/M) capacitor. In particular, we examine a Au/IL/Au structure where the IL is 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate. The experiments consist of frequency-dependent impedance measurements and time-dependent current vs voltage measurements for applied linear voltage ramps and abrupt voltage steps. The parameters of an equivalent circuit model are determined by fits to the impedance vs frequency data and subsequently verified by calculating the current vs voltage characteristics for the applied potential profiles. The data analysis indicates that the dynamics of the structure are characterized by a wide distribution of relaxation times spanning the range of less than microseconds to longer than seconds. Possible causes for these time scales are discussed.

Ionic liquid gating on atomic layer deposition passivated GaN: Ultra-high electron density induced high drain current and low contact resistance

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

Zhou, Hong; Du, Yuchen; Ye, Peide D., E-mail: yep@purdue.edu

2016-05-16

Herein, we report on achieving ultra-high electron density (exceeding 10{sup 14 }cm{sup −2}) in a GaN bulk material device by ionic liquid gating, through the application of atomic layer deposition (ALD) of Al{sub 2}O{sub 3} to passivate the GaN surface. Output characteristics demonstrate a maximum drain current of 1.47 A/mm, the highest reported among all bulk GaN field-effect transistors, with an on/off ratio of 10{sup 5} at room temperature. An ultra-high electron density exceeding 10{sup 14 }cm{sup −2} accumulated at the surface is confirmed via Hall-effect measurement and transfer length measurement. In addition to the ultra-high electron density, we also observe a reductionmore » of the contact resistance due to the narrowing of the Schottky barrier width on the contacts. Taking advantage of the ALD surface passivation and ionic liquid gating technique, this work provides a route to study the field-effect and carrier transport properties of conventional semiconductors in unprecedented ultra-high charge density regions.« less

Ohmic model for electrodeposition of metallic ions

NASA Astrophysics Data System (ADS)

Gliozzi, A. S.; Alexe-Ionescu, A. L.; Barbero, G.

2015-10-01

An ohmic model to describe the electrodeposition of metallic ions on the electrodes is proposed. We assume that the ionic distribution is homogeneous across the electrolytic cell, and that the ionic current is due to the bulk electric field. The nucleation in the electrodeposition is supposed to be well described by a kinetic equation at the electrode, taking into account the neutralization of metallic ions on the electrodes. Two cases are considered. In the first case the characteristic time describing the neutralization of the ions is supposed to be negligible with respect to the flight time of the ions across the cell. In this framework the bulk electric field coincides with the external electric field, and our analysis gives analytical formulae for the surface density of deposited ions and for the electric current in the external circuit. The case where the two characteristic times are comparable, and the effective electric field in the bulk depends on the surface deposition, is considered too. In this case the ordinary differential equations describing the ionic distribution and the adsorption phenomenon have to be solved numerically. The agreement between the presented model and the experimental results published by several groups is reasonably good.

Design of Energetic Ionic Liquids

DTIC Science & Technology

2007-06-01

associated polarizable force fields, and mesoscale-level simulations with currently usedpropellants. of bulk ionic liquids based upon multiscale coarse A...pair. The 1H,3H cation paired with perchlorate ( nitrate ) has a proton transfer barrier of 2.7 0.08w ’I (3.0) kcal/mol. /.04 - M K I 373K<[Emimlllm-l Ion...series of ion clusters [Emim+]m[Im’]mn± 4-amino- 1,2,4-triazolium nitrate (HEATN) have (m=l-3) were computed using the hybrid B3LYP density identified a

Electrodeposition and characterisation of Al-W alloy films from ionic liquid

NASA Astrophysics Data System (ADS)

Höhlich, D.; Wachner, D.; Müller, M.; Scharf, I.; Lampke, T.

2018-06-01

Al–W alloy films were prepared by electrodeposition using anhydrous 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic-liquid solution with aluminium chloride in a ratio of 1:1.5. As a commercially available tungsten precursor, tungsten hexachloride was used. The metal is dissolved in the ionic liquid at concentrations up to 0.06 mol/l. The deposition took place outside the glove box with a continuous argon stream over the electrolyte at a temperature of 60 °C with a current density of 1 A/m2. Resulting alloys show a tungsten content higher than 20 wt% (3.5 at%). The phase composition of Al-W alloys was observed by X-ray diffraction (XRD), and the chemical composition was characterised by scanning electron microscopy (SEM) and inductively-coupled plasma optical emission spectroscopy (ICP-OES).

The thiocyanate anion is a primary driver of carbon dioxide capture by ionic liquids

NASA Astrophysics Data System (ADS)

Chaban, Vitaly

2015-01-01

Carbon dioxide, CO2, capture by room-temperature ionic liquids (RTILs) is a vivid research area featuring both accomplishments and frustrations. This work employs the PM7-MD method to simulate adsorption of CO2 by 1,3-dimethylimidazolium thiocyanate at 300 K. The obtained result evidences that the thiocyanate anion plays a key role in gas capture, whereas the impact of the 1,3-dimethylimidazolium cation is mediocre. Decomposition of the computed wave function on the individual molecular orbitals confirms that CO2-SCN binding extends beyond just expected electrostatic interactions in the ion-molecular system and involves partial sharing of valence orbitals.

A correlation between extensional displacement and architecture of ionic polymer transducers

NASA Astrophysics Data System (ADS)

Akle, Barbar J.; Duncan, Andrew; Leo, Donald J.

2008-03-01

Ionic polymer transducers (IPT), sometimes referred to as artificial muscles, are known to generate a large bending strain and a moderate stress at low applied voltages (<5V). Bending actuators have limited engineering applications due to the low forcing capabilities and the need for complicated external devices to convert the bending action into rotating or linear motion desired in most devices. Recently Akle and Leo reported extensional actuation in ionic polymer transducers. In this study, extensional IPTs are characterized as a function of transducer architecture. In this study 2 actuators are built and there extensional displacement response is characterized. The transducers have similar electrodes while the middle membrane in the first is a Nafion / ionic liquid and an aluminum oxide - ionic liquid in the second. The first transducer is characterized for constant current input, voltage step input, and sweep voltage input. The model prediction is in agreement in both shape and magnitude for the constant current experiment. The values of α and β used are within the range of values reported in Akle and Leo. Both experiments and model demonstrate that there is a preferred direction of applying the potential so that the transducer will exhibit large deformations. In step response the model well predicted the negative potential and the early part of the step in the positive potential and failed to predict the displacement after approximately 180s has elapsed. The model well predicted the sweep response, and the observed 1st harmonic in the displacement further confirmed the existence of a quadratic in the charge response. Finally the aluminum oxide based transducer is characterized for a step response and compared to the Nafion based transducer. The second actuator demonstrated electromechanical extensional response faster than that in the Nafion based transducer. The Aluminum oxide based transducer is expected to provide larger forces and hence larger energy density.

Enhanced photoluminescence from single nitrogen-vacancy defects in nanodiamonds coated with phenol-ionic complexes

NASA Astrophysics Data System (ADS)

Bray, Kerem; Previdi, Rodolfo; Gibson, Brant C.; Shimoni, Olga; Aharonovich, Igor

2015-03-01

Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications.Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07510b

Calculation of ionized fields in DC electrostatic precipitators in the presence of dust and electric wind

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

Cristina, S.; Feliziani, M.

1995-11-01

This paper describes a new procedure for the numerical computation of the electric field and current density distributions in a dc electrostatic precipitator in the presence of dust, taking into account the particle-size distribution. Poisson`s and continuity equations are numerically solved by supposing that the coronating conductors satisfy Kaptzov`s assumption on the emitter surfaces. Two iterative numerical procedures, both based on the finite element method (FEM), are implemented for evaluating, respectively, the unknown ionic charge density and the particle charge density distributions. The V-I characteristic and the precipitation efficiencies for the individual particle-size classes, calculated with reference to the pilotmore » precipitator installed by ENEL (Italian Electricity Board) at its Marghera (Venice) coal-fired power station, are found to be very close to those measured experimentally.« less

Single Protein Structural Analysis with a Solid-state Nanopore Sensor

NASA Astrophysics Data System (ADS)

Li, Jiali; Golovchenko, Jene; McNabb, David

2005-03-01

We report on the use of solid-state nanopore sensors to detect single polypeptides. These solid-state nanopores are fabricated in thin membranes of silicon nitride by ion beam sculpting...[1]. When an electrically biased nanopore is exposed to denatured proteins in ionic solution, discrete transient electronic signals: current blockages are observed. We demonstrate examples of such transient electronic signals for Bovine Serum Albumin (BSA) and human placental laminin M proteins in Guanidine hydrochloride solution, which suggest that these polypeptides are individually translocating through the nanopore during the detecting process. The amplitude of the current blockages is proportional to the bias voltage. No transient current blockages are observed when proteins are not present in the solution. To probe protein-folding state, pH and temperature dependence experiments are performed. The results demonstrate a solid-state nanopore sensor can be used to detect and analyze single polypeptide chains. Similarities and differences with signals obtained from double stranded DNA in a solid-state nanopore and single stranded DNA in a biological nanopore are discussed. [.1] Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169.

Single molecule detection with graphene and other two-dimensional materials: nanopores and beyond

PubMed Central

Arjmandi-Tash, Hadi; Belyaeva, Liubov A.

2016-01-01

Graphene and other two dimensional (2D) materials are currently integrated into nanoscaled devices that may – one day – sequence genomes. The challenge to solve is conceptually straightforward: cut a sheet out of a 2D material and use the edge of the sheet to scan an unfolded biomolecule from head to tail. As the scan proceeds – and because 2D materials are atomically thin – the information provided by the edge might be used to identify different segments – ideally single nucleotides – in the biomolecular strand. So far, the most efficient approach was to drill a nano-sized pore in the sheet and use this pore as a channel to guide and detect individual molecules by measuring the electrochemical ionic current. Nanoscaled gaps between two electrodes in 2D materials recently emerged as powerful alternatives to nanopores. This article reviews the current status and prospects of integrating 2D materials in nanopores, nanogaps and similar devices for single molecule biosensing applications. We discuss the pros and cons, the challenges, and the latest achievements in the field. To achieve high-throughput sequencing with 2D materials, interdisciplinary research is essential. PMID:26612268

Observed mechanism for the breakup of small bundles of cellulose Iα and Iβ in ionic liquids from molecular dynamics simulations.

PubMed

Rabideau, Brooks D; Agarwal, Animesh; Ismail, Ahmed E

2013-04-04

Explicit, all-atom molecular dynamics simulations are used to study the breakup of small bundles of cellulose Iα and Iβ in the ionic liquids [BMIM]Cl, [EMIM]Ac, and [DMIM]DMP. In all cases, significant breakup of the bundles is observed with the initial breakup following a common underlying mechanism. Anions bind strongly to the hydroxyl groups of the exterior strands of the bundle, forming negatively charged complexes. Binding also weakens the intrastrand hydrogen bonds present in the cellulose strands, providing greater strand flexibility. Cations then intercalate between the individual strands, likely due to charge imbalances, providing the bulk to push the individual moieties apart and initiating the separation. The peeling of an individual strand from the main bundle is observed in [EMIM]Ac with an analysis of its hydrogen bonds with other strands showing that the chain detaches glucan by glucan from the main bundle in discrete, rapid events. Further analysis shows that the intrastrand hydrogen bonds of each glucan tend to break for a sustained period of time before the interstrand hydrogen bonds break and strand detachment occurs. Examination of similar nonpeeling strands shows that, without this intrastrand hydrogen bond breakage, the structural rigidity of the individual unit can hinder its peeling despite interstrand hydrogen bond breakage.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

First spectroscopic identification of pyrocarbonate for high CO2 flux membranes containing highly interconnected three dimensional ionic channels.

PubMed

Zhang, Lingling; Huang, Xinyu; Qin, Changyong; Brinkman, Kyle; Gong, Yunhui; Wang, Siwei; Huang, Kevin

2013-08-21

Identification of the existence of pyrocarbonate ion C2O5(2-) in molten carbonates exposed to a CO2 atmosphere provides key support for a newly established bi-ionic transport model that explains the mechanisms of high CO2 permeation flux observed in mixed oxide-ion and carbonate-ion conducting (MOCC) membranes containing highly interconnected three dimensional ionic channels. Here we report the first Raman spectroscopic evidence of C2O5(2-) as an active species involved in the CO2-transport process of MOCC membranes exposed to a CO2 atmosphere. The two new broad peaks centered at 1317 cm(-1) and 1582 cm(-1) are identified as the characteristic frequencies of the C2O5(2-) species. The measured characteristic Raman frequencies of C2O5(2-) are in excellent agreement with the DFT-model consisting of six overlapping individual theoretical bands calculated from Li2C2O5 and Na2C2O5.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

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

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Bone as an ion exchange system: evidence for a link between mechanotransduction and metabolic needs.

PubMed

Rubinacci, A; Covini, M; Bisogni, C; Villa, I; Galli, M; Palumbo, C; Ferretti, M; Muglia, M A; Marotti, G

2002-04-01

To detect whether the mutual interaction occurring between the osteocytes-bone lining cells system (OBLCS) and the bone extracellular fluid (BECF) is affected by load through a modification of the BECF-extracellular fluid (ECF; systemic extracellular fluid) gradient, mice metatarsal bones immersed in ECF were subjected ex vivo to a 2-min cyclic axial load of different amplitudes and frequencies. The electric (ionic) currents at the bone surface were measured by a vibrating probe after having exposed BECF to ECF through a transcortical hole. The application of different loads and different frequencies increased the ionic current in a dose-dependent manner. The postload current density subsequently decayed following an exponential pattern. Postload increment's amplitude and decay were dependent on bone viability. Dummy and static loads did not induce current density modifications. Because BECF is perturbed by loading, it is conceivable that OBLCS tends to restore BECF preload conditions by controlling ion fluxes at the bone-plasma interface to fulfill metabolic needs. Because the electric current reflects the integrated activity of OBLCS, its evaluation in transgenic mice engineered to possess genetic lesions in channels or matrix constituents could be helpful in the characterization of the mechanical and metabolic functions of bone.

Dynamic reciprocity of sodium and potassium channel expression in a macromolecular complex controls cardiac excitability and arrhythmia.

PubMed

Milstein, Michelle L; Musa, Hassan; Balbuena, Daniela Ponce; Anumonwo, Justus M B; Auerbach, David S; Furspan, Philip B; Hou, Luqia; Hu, Bin; Schumacher, Sarah M; Vaidyanathan, Ravi; Martens, Jeffrey R; Jalife, José

2012-07-31

The cardiac electrical impulse depends on an orchestrated interplay of transmembrane ionic currents in myocardial cells. Two critical ionic current mechanisms are the inwardly rectifying potassium current (I(K1)), which is important for maintenance of the cell resting membrane potential, and the sodium current (I(Na)), which provides a rapid depolarizing current during the upstroke of the action potential. By controlling the resting membrane potential, I(K1) modifies sodium channel availability and therefore, cell excitability, action potential duration, and velocity of impulse propagation. Additionally, I(K1)-I(Na) interactions are key determinants of electrical rotor frequency responsible for abnormal, often lethal, cardiac reentrant activity. Here, we have used a multidisciplinary approach based on molecular and biochemical techniques, acute gene transfer or silencing, and electrophysiology to show that I(K1)-I(Na) interactions involve a reciprocal modulation of expression of their respective channel proteins (Kir2.1 and Na(V)1.5) within a macromolecular complex. Thus, an increase in functional expression of one channel reciprocally modulates the other to enhance cardiac excitability. The modulation is model-independent; it is demonstrable in myocytes isolated from mouse and rat hearts and with transgenic and adenoviral-mediated overexpression/silencing. We also show that the post synaptic density, discs large, and zonula occludens-1 (PDZ) domain protein SAP97 is a component of this macromolecular complex. We show that the interplay between Na(v)1.5 and Kir2.1 has electrophysiological consequences on the myocardium and that SAP97 may affect the integrity of this complex or the nature of Na(v)1.5-Kir2.1 interactions. The reciprocal modulation between Na(v)1.5 and Kir2.1 and the respective ionic currents should be important in the ability of the heart to undergo self-sustaining cardiac rhythm disturbances.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore

NASA Astrophysics Data System (ADS)

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2016-09-01

A stable nanoscale thermal hot spot, with temperature approaching 100 °C , is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z , collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore.

PubMed

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2016-09-23

A stable nanoscale thermal hot spot, with temperature approaching 100 °C, is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z, collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

PubMed

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-03-16

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.

Fabrication of Nanochannels

PubMed Central

Zhang, Yuqi; Kong, Xiang-Yu; Gao, Loujun; Tian, Ye; Wen, Liping; Jiang, Lei

2015-01-01

Nature has inspired the fabrication of intelligent devices to meet the needs of the advanced community and better understand the imitation of biology. As a biomimetic nanodevice, nanochannels/nanopores aroused increasing interest because of their potential applications in nanofluidic fields. In this review, we have summarized some recent results mainly focused on the design and fabrication of one-dimensional nanochannels, which can be made of many materials, including polymers, inorganics, biotic materials, and composite materials. These nanochannels have some properties similar to biological channels, such as selectivity, voltage-dependent current fluctuations, ionic rectification current and ionic gating, etc. Therefore, they show great potential for the fields of biosensing, filtration, and energy conversions. These advances can not only help people to understand the living processes in nature, but also inspire scientists to develop novel nanodevices with better performance for mankind. PMID:28793564

Inorganic nanotubes and electro-fluidic devices fabricated therefrom

DOEpatents

Yang, Peidong [Kensington, CA; Majumdar, Arunava [Orinda, CA; Fan, Rong [Pasadena, CA; Karnik, Rohit [Cambridge, MA

2011-03-01

Nanofluidic devices incorporating inorganic nanotubes fluidly coupled to channels or nanopores for supplying a fluid containing chemical or bio-chemical species are described. In one aspect, two channels are fluidly interconnected with a nanotube. Electrodes on opposing sides of the nanotube establish electrical contact with the fluid therein. A bias current is passed between the electrodes through the fluid, and current changes are detected to ascertain the passage of select molecules, such as DNA, through the nanotube. In another aspect, a gate electrode is located proximal the nanotube between the two electrodes thus forming a nanofluidic transistor. The voltage applied to the gate controls the passage of ionic species through the nanotube selected as either or both ionic polarities. In either of these aspects the nanotube can be modified, or functionalized, to control the selectivity of detection or passage.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties

PubMed Central

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-01-01

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. PMID:26999112

Recent progress in biopolymer nanoparticle and microparticle formation by heat-treating electrostatic protein-polysaccharide complexes.

PubMed

Jones, Owen G; McClements, David Julian

2011-09-14

Functional biopolymer nanoparticles or microparticles can be formed by heat treatment of globular protein-ionic polysaccharide electrostatic complexes under appropriate solution conditions. These biopolymer particles can be used as encapsulation and delivery systems, fat mimetics, lightening agents, or texture modifiers. This review highlights recent progress in the design and fabrication of biopolymer particles based on heating globular protein-ionic polysaccharide complexes above the thermal denaturation temperature of the proteins. The influence of biopolymer type, protein-polysaccharide ratio, pH, ionic strength, and thermal history on the characteristics of the biopolymer particles formed is reviewed. Our current understanding of the underlying physicochemical mechanisms of particle formation and properties is given. The information provided in this review should facilitate the rational design of biopolymer particles with specific physicochemical and functional attributes, as well as stimulate further research in identifying the physicochemical origin of particle formation. Copyright © 2010 Elsevier B.V. All rights reserved.

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub-Nanoporous Materials.

PubMed

Sakamoto, Takeshi; Ogawa, Takafumi; Nada, Hiroki; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro; Henmi, Masahiro; Kato, Takashi

2018-01-01

Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self-organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self-organized sub-nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub-nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability.

Alkali Metal-Glucose Interaction Probed with Infrared Pre-Dissociation Spectroscopy

NASA Astrophysics Data System (ADS)

Kregel, Steven J.; Marsh, Brett; Zhou, Jia; Garand, Etienne

2015-06-01

The efficient extraction of cellulose from biomass and its subsequent conversion to glucose derivatives is an attractive goal in the field of energy science. However, current industrial methods require high ionic strength and harsh conditions. Ionic liquids (IL's) are a class of "green" compounds that have been shown to dissolve cellulose in concentrations of up to 25 wt%. In order to understand IL's extraordinary cellulose dissolving power, a molecular level understanding of the IL-cellulose interaction is needed. Toward that end, we have acquired infrared pre-dissociation spectra of M+-glucose, where M+=Li+, Na+, or K+. Through comparisons with density functional theory calculations, we have determined the relative abundances of various M+-glucose binding motifs in both the thermodynamic and kinetic limits. These results provide insight on the hydrogen bonding dynamics of glucose and are a step towards a fuller understanding of cellulose interactions with ionic liquids.

Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

PubMed

Kwon, Taehoon; Cho, Hyeongrae; Lee, Jang-Woo; Henkensmeier, Dirk; Kang, Youngjong; Koo, Chong Min

2017-08-30

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H + /g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm -1 ), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m -3 ) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

NASA Astrophysics Data System (ADS)

Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

2014-03-01

We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub‐Nanoporous Materials

PubMed Central

Ogawa, Takafumi; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro

2017-01-01

Abstract Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self‐organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self‐organized sub‐nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub‐nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability. PMID:29375969

Ionic blockade of the rat connexin40 gap junction channel by large tetraalkylammonium ions.

PubMed

Musa, H; Gough, J D; Lees, W J; Veenstra, R D

2001-12-01

The rat connexin40 gap junction channel is permeable to monovalent cations including tetramethylammonium and tetraethylammonium ions. Larger tetraalkyammonium (TAA(+)) ions beginning with tetrabutylammonium (TBA(+)) reduced KCl junctional currents disproportionately. Ionic blockade by tetrapentylammonium (TPeA(+)) and tetrahexylammonium (THxA(+)) ions were concentration- and voltage-dependent and occurred only when TAA(+) ions were on the same side as net K(+) efflux across the junction, indicative of block of the ionic permeation pathway. The voltage-dependent dissociation constants (K(m)(V(j))) were lower for THxA(+) than TPeA(+), consistent with steric effects within the pore. The K(m)-V(j) relationships for TPeA(+) and THxA(+) were fit with different reaction rate models for a symmetrical (homotypic) connexin gap junction channel and were described by either a one- or two-site model that assumed each ion traversed the entire V(j) field. Bilateral addition of TPeA(+) ions confirmed a common site of interaction within the pore that possessed identical K(m)(V(j)) values for cis-trans concentrations of TPeA(+) ions as indicated by the modeled I-V relations and rapid channel block that precluded unitary current measurements. The TAA(+) block of K(+) currents and bilateral TPeA(+) interactions did not alter V(j)-gating of Cx40 gap junctions. N-octyl-tributylammonium and -triethylammonium also blocked rCx40 channels with higher affinity and faster kinetics than TBA(+) or TPeA(+), indicative of a hydrophobic site within the pore near the site of block.

Composition of nasal airway surface liquid in cystic fibrosis and other airway diseases determined by X-ray microanalysis.

PubMed

Vanthanouvong, V; Kozlova, I; Johannesson, M; Nääs, E; Nordvall, S L; Dragomir, A; Roomans, G M

2006-04-01

The ionic composition of the airway surface liquid (ASL) in healthy individuals and in patients with cystic fibrosis (CF) has been debated. Ion transport properties of the upper airway epithelium are similar to those of the lower airways and it is easier to collect nasal ASL from the nose. ASL was collected with ion exchange beads, and the elemental composition of nasal fluid was determined by X-ray microanalysis in healthy subjects, CF patients, CF heterozygotes, patients with rhinitis, and with primary ciliary dyskinesia (PCD). In healthy subjects, the ionic concentrations were approximately isotonic. In CF patients, CF heterozygotes, rhinitis, and PCD patients, [Na] and [Cl] were significantly higher compared when compared with those in controls. [K] was significantly higher in CF and PCD patients compared with that in controls. Severely affected CF patients had higher ionic concentrations in their nasal ASL than in patients with mild or moderate symptoms. Female CF patients had higher levels of Na, Cl, and K than male patients. As higher salt concentrations in the ASL are also found in other patients with airway diseases involving chronic inflammation, it appears likely that inflammation-induced epithelial damage is important in determining the ionic composition of the ASL. Copyright (c) 2006 Wiley-Liss, Inc.

Removal of total cyanide in coking wastewater during a coagulation process: significance of organic polymers.

PubMed

Shen, Jian; Zhao, He; Cao, Hongbin; Zhang, Yi; Chen, Yongsheng

2014-02-01

Whether a cationic organic polymer can remove more total cyanide (TCN) than a non-ionic organic polymer during the same flocculation system has not been reported previously. In this study, the effects of organic polymers with different charge density on the removal mechanisms of TCN in coking wastewater are investigated by polyferric sulfate (PFS) with a cationic organic polymer (PFS-C) or a non-ionic polymer (PFS-N). The coagulation experiments results show that residual concentrations of TCN (Fe(CN)6(3-)) after PFS-C flocculation (TCN < 0.2 mg/L) are much lower than that after PFS-N precipitation. This can be attributed to the different TCN removal mechanisms of the individual organic polymers. To investigate the roles of organic polymers, physical and structural characteristics of the flocs are analyzed by FT-IR, XPS, TEM and XRD. Owing to the presence of N+ in PFS-C, Fe(CN)6(3-) and negative flocs (Fe(CN)6(3-) adsorbed on ferric hydroxides) can be removed via charge neutralization and electrostatic patch flocculation by the cationic organic polymer. However, non-ionic N in PFS-N barely reacts with cyanides through sweeping or bridging, which indicates that the non-ionic polymer has little influence on TCN removal.

Fabrication of fiber supported ionic liquids and methods of use

DOEpatents

Luebke, David R; Wickramanayake, Shan

2013-02-26

One or more embodiments relates to the production of a fabricated fiber having an asymmetric polymer network and having an immobilized liquid such as an ionic liquid within the pores of the polymer network. The process produces the fabricated fiber in a dry-wet spinning process using a homogenous dope solution, providing significant advantage over current fabrication methods for liquid-supporting polymers. The fabricated fibers may be effectively utilized for the separation of a chemical species from a mixture based on the selection of the polymer, the liquid, and the solvent utilized in the dope.

A network thermodynamic method for numerical solution of the Nernst-Planck and Poisson equation system with application to ionic transport through membranes.

PubMed

Horno, J; González-Caballero, F; González-Fernández, C F

1990-01-01

Simple techniques of network thermodynamics are used to obtain the numerical solution of the Nernst-Planck and Poisson equation system. A network model for a particular physical situation, namely ionic transport through a thin membrane with simultaneous diffusion, convection and electric current, is proposed. Concentration and electric field profiles across the membrane, as well as diffusion potential, have been simulated using the electric circuit simulation program, SPICE. The method is quite general and extremely efficient, permitting treatments of multi-ion systems whatever the boundary and experimental conditions may be.

Rapid Polymer Transport in a Single Nanometer-Scale Pore

NASA Astrophysics Data System (ADS)

Kasianowicz, J. J.

1998-03-01

Protein ion channels are nanometer-scale pores that control the transport of ions and polymers across cell membranes. We compared the ability of charged and nonelectrolyte linear polymers to partition into a single channel reconstituted into a planar lipid bilayer membrane. The entry of each polymer (e.g. monodisperse length single-stranded homopolymeric RNA1 or poly(ethylene glycol)2,3) into the pore caused characteristic transient decreases in the channel's ionic conductance. The ionic current blockades yield detailed information about the physical properties of the polymers and the pore. The biological and technological significance of the results will be discussed.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

2005-11-01

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Electrostatic energy of transfer and macrobond analyses of intermolecular interactions and hydration effects in protein crystals in a low ionic environment

NASA Astrophysics Data System (ADS)

Sugawara, Yoko; Hirano, Yuji; Yamamura, Shigefumi; Endo, Shigeru; Ootaki, Masanori; Matsumoto, Naoki; Takahashi, Takuya

2017-06-01

We developed an electrostatic energy of transfer (EET) analysis applicable to periodic boundary condition, including a nonrectangular unit cell. It was applied to monoclinic ribonuclease A crystallized with ethanol as a precipitant. Macrobond analysis was also carried out. Owing to the low ionic strength of the solvent region, atomic EET values were non-negligible even at long-distance points. Most of the molecular EET values-defined as the individual contribution of each surrounding molecule-were positive. The inclusion of the molecular EET values of hydration water molecules reduced the repulsive force, and the evaluation of hydration effects in protein crystals was found to be imperative.

Enhanced photoluminescence from single nitrogen-vacancy defects in nanodiamonds coated with phenol-ionic complexes.

PubMed

Bray, Kerem; Previdi, Rodolfo; Gibson, Brant C; Shimoni, Olga; Aharonovich, Igor

2015-03-21

Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications.

Theoretical model of the ionic mechanism of 1/f noise in nerve membrane.

PubMed Central

Clay, J R; Shlesinger, M F

1976-01-01

A model is presented for the ionic mechanism of low frequency 1/f electrical noise which has been observed in axonal membranes. The model consists of narrow channels which open randomly throughout the membrane and remain open for only a short time compared with f-1max where fmax approximately 2 kHz is the maximum frequency for which 1/f noise is observed. The fluctuation in channel formation is coupled to low frequency normal mode vibrations in liquid crystals which have properties similar to nerve membranes. Ionic current flow through the channels is assumed to occur via single file diffusion. The diffusion process is regarded as a non-Markovian random walk on a one-dimensional lattice which is mathematically decomposed into its spatial and temporal components. This technique allows calculation of the mean and variance of the number of ions which flow through any single short-lived channel. The final result for the current noise power spectrum, S, is S(f) = (A + k/I/2)/f, where I is the mean membrane current and A and k are parameters which are independent of membrane voltage. The theoretical result is consistent with observations of 1/f noise in lobster axon by Poussart (1971, Biophys. J. 11:212.) on the dependence of S(f) on the mean steady-state current and the external potassium concentration. We also calculate the mean channel density and the Frank elastic constant of the membrane. This work is an extension of a macroscopic model of Lundström and McQueen (1974, J. Theor. Biol. 45:405.) who obtain a spectral density of the form S approximately /I/2/f. PMID:1247642

Polyamines Interact with Hydroxyl Radicals in Activating Ca2+ and K+ Transport across the Root Epidermal Plasma Membranes1[W

PubMed Central

Zepeda-Jazo, Isaac; Velarde-Buendía, Ana María; Enríquez-Figueroa, René; Bose, Jayakumar; Shabala, Sergey; Muñiz-Murguía, Jesús; Pottosin, Igor I.

2011-01-01

Reactive oxygen species (ROS) are integral components of the plant adaptive responses to environment. Importantly, ROS affect the intracellular Ca2+ dynamics by activating a range of nonselective Ca2+-permeable channels in plasma membrane (PM). Using patch-clamp and noninvasive microelectrode ion flux measuring techniques, we have characterized ionic currents and net K+ and Ca2+ fluxes induced by hydroxyl radicals (OH•) in pea (Pisum sativum) roots. OH•, but not hydrogen peroxide, activated a rapid Ca2+ efflux and a more slowly developing net Ca2+ influx concurrent with a net K+ efflux. In isolated protoplasts, OH• evoked a nonselective current, with a time course and a steady-state magnitude similar to those for a K+ efflux in intact roots. This current displayed a low ionic selectivity and was permeable to Ca2+. Active OH•-induced Ca2+ efflux in roots was suppressed by the PM Ca2+ pump inhibitors eosine yellow and erythrosine B. The cation channel blockers gadolinium, nifedipine, and verapamil and the anionic channel blockers 5-nitro-2(3-phenylpropylamino)-benzoate and niflumate inhibited OH•-induced ionic currents in root protoplasts and K+ efflux and Ca2+ influx in roots. Contrary to expectations, polyamines (PAs) did not inhibit the OH•-induced cation fluxes. The net OH•-induced Ca2+ efflux was largely prolonged in the presence of spermine, and all PAs tested (spermine, spermidine, and putrescine) accelerated and augmented the OH•-induced net K+ efflux from roots. The latter effect was also observed in patch-clamp experiments on root protoplasts. We conclude that PAs interact with ROS to alter intracellular Ca2+ homeostasis by modulating both Ca2+ influx and efflux transport systems at the root cell PM. PMID:21980172

Treatment with the non-ionic surfactant poloxamer P188 reduces DNA fragmentation in cells from bovine chondral explants exposed to injurious unconfined compression.

PubMed

Baars, D C; Rundell, S A; Haut, R C

2006-06-01

Excessive mechanical loading to a joint has been linked with the development of post-traumatic osteoarthritis (OA). Among the suspected links between impact trauma to a joint and associated degeneration of articular cartilage is an acute reduction in chondrocyte viability. Recently, the non-ionic surfactant poloxamer 188 (P188) has been shown to reduce by approximately 50% the percentage of non-viable chondrocytes 24 h post-injury in chondral explants exposed to 25 MPa of unconfined compression. There is a question whether these acutely 'saved' chondrocytes will continue to degrade over time, as P188 is only thought to act by acute repair of damaged cell membranes. In order to investigate the degradation of traumatized chondrocytes in the longer term, the current study utilized TUNEL staining to document the percentage of cells suffering DNA fragmentation with and without an immediate 24 h period of exposure of the explants to P188 surfactant. In the current study, as in the previous study by this laboratory, chondral explants were excised from bovine metacarpophalangeal joints and subjected to 25 MPa of unconfined compression. TUNEL staining was performed at 1 h, 4 days, and 7 days post-impact. The current study found that P188 was effective in reducing the percentage of cells with DNA fragmentation in impacted explants by approximately 45% at 4 and 7 days post-impact. These data suggest that early P188 intervention was effective in preventing DNA fragmentation of injured chondrocytes. The current hypothesis is that this process was mitigated by the acute repair of damaged plasma membranes by the non-ionic surfactant P188, and that most repaired cells did not continue to degrade as measured by the fragmentation of their DNA.

The Sensitive Side of Galaxy Formation: How sub-L* Galaxies Accrete, Form Stars, and Enrich the IGM

NASA Astrophysics Data System (ADS)

Oppenheimer, Benjamin

2012-10-01

We propose a series of cosmological zoom simulations specifically targeting the formation and evolution of dwarf and sub-L* galaxies living in halos of 10^11- 10^12 solar masses. The shallow potential wells and low-density environments of these halos provide uniquely sensitive laboratories to understand the physics of galactic feedback, as well as the thermal history of the intergalactic medium, from which these galaxies accrete. Given that 129 orbits of Cycle 18 COS data probing such halos is now being completed, combined with the insufficiency of current cosmological simulations to resolve these halos, the theory is lagging the data. We will remedy this by running zoom simulations of individual halos with 1000-10,000 times greater mass resolution than current cosmological simulations used for similar studies. We aim to resolve the sub-kpc scale of high-velocity cloud-like structures and <100 pc scales of the interstellar medium. We will simulate circumgalactic quasar absorption metal-line and H I statistics using our novel non-equilibrium ionization solver that follows individual ionic states. We will also investigate the delicate balance of accretion, star formation, and feedback required to reproduce the observed stellar properties of these small galaxies. In the spirit of transparency, we will make our simulation results available on a public website to encourage new projects and collaborations with observers and theorists understanding the physics regulating galaxy growth.

Fast-slow asymptotics for a Markov chain model of fast sodium current

NASA Astrophysics Data System (ADS)

Starý, Tomáš; Biktashev, Vadim N.

2017-09-01

We explore the feasibility of using fast-slow asymptotics to eliminate the computational stiffness of discrete-state, continuous-time deterministic Markov chain models of ionic channels underlying cardiac excitability. We focus on a Markov chain model of fast sodium current, and investigate its asymptotic behaviour with respect to small parameters identified in different ways.

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

NASA Astrophysics Data System (ADS)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Theoretical interpretation of the limiting electric conductivity in ionic solution

NASA Astrophysics Data System (ADS)

Fraenkel, Dan

2017-12-01

The physical essence of the limiting equivalent ionic conductivity in solution, λ0i, has been a continuing challenge over almost a century. Here I briefly present an ab initio theoretical treatment providing (1) a new insight into the nature of λ0i, and (2) a mathematical formula for computing λ0i. In the new treatment, one assumes that any chosen ion i is surrounded by a spherical body of oriented solvent dipoles carrying the charge of the counterion, and the bulk solvent is a continuum with no molecular detail. λ0i is thus the result of the tandem operation, at hydrodynamic equilibrium, of the dipole body's electrophoretic and relaxation forces exerted on the drifting ion. λ0i is found to be proportional to the radius of ion i, and independent of the ionic charge. From experimental λ0i's, the ion radius can be computed as 'electric radius.' An electric ion-radius scale so derived compares well with other ion-size scales. The current theory expresses λ0i using only universal constants and unitary factors of the ionic solution, and it sheds new light on the fundamental nature of ion and charge transport in a polar liquid medium.

[Influence of non-ionic surfactants on sludge dewaterability].

PubMed

Hou, Hai-Pan; Pu, Wen-Hong; Shi, Ya-Fei; Yu, Wen-Hua; Fan, Ming-Ming; Liu, Huan; Yang, Chang-Zhu; Li, Ye; Yang, Jia-Kuan

2012-06-01

The water content of dewatered sludge cake decreases to about 80% by current sludge dewatering technologies, which hardly satisfies the stricter standards of sludge disposal. In order to evaluate the effects of non-ionic surfactants on sludge dewaterability, two kinds of non-ionic surfactants (OPEO and APG) were studied by using two evaluation indexes, i. e. , specific resistance to filtration (SRF) and dewatering efficiency. Moreover, morphologies of conditioned sewage sludge and raw sludge were comparatively investigated. Results showed that non-ionic surfactants can decrease the particle size of sewage sludge floc and generate more homogenous and regular shape, and then improve the dewatering efficiency. APG has better effect on sewage sludge dewatering than OPEO. SRF of conditioned sludge with APG dosage of 0.05% DS decreased to 42% of SRF of raw sludge, and its dewatering efficiency was as high as 93%. Plate-frame pressure filter experiment demonstrated that, the water content of dewatered cake conditioned with APG dosage of 0.05% DS was lower by about 10% than that of dewatered cake without APG, and its dewatering efficiency reached 97%. Therefore, this research provides some reference for the application of APG in sludge dewatering.

Piezoelectric transformers for low-voltage generation of gas discharges and ionic winds in atmospheric air

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

Johnson, Michael J.; Go, David B., E-mail: dgo@nd.edu; Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indianapolis 46556

To generate a gas discharge (plasma) in atmospheric air requires an electric field that exceeds the breakdown threshold of ∼30 kV/cm. Because of safety, size, or cost constraints, the large applied voltages required to generate such fields are often prohibitive for portable applications. In this work, piezoelectric transformers are used to amplify a low input applied voltage (<30 V) to generate breakdown in air without the need for conventional high-voltage electrical equipment. Piezoelectric transformers (PTs) use their inherent electromechanical resonance to produce a voltage amplification, such that the surface of the piezoelectric exhibits a large surface voltage that can generate corona-like dischargesmore » on its corners or on adjacent electrodes. In the proper configuration, these discharges can be used to generate a bulk air flow called an ionic wind. In this work, PT-driven discharges are characterized by measuring the discharge current and the velocity of the induced ionic wind with ionic winds generated using input voltages as low as 7 V. The characteristics of the discharge change as the input voltage increases; this modifies the resonance of the system and subsequent required operating parameters.« less

High-Surface-Area CO2 Sponge: High Performance CO2 Scrubbing Based on Hollow Fiber-Supported Designer Ionic Liquid Sponges

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

None

IMPACCT Project: The team from ORNL and Georgia Tech is developing a new technology that will act like a sponge, integrating a new, alcohol-based ionic liquid into hollow fibers (magnified image, right) to capture CO2 from the exhaust produced by coal-fired power plants. Ionic liquids, or salts that exist in liquid form, are promising materials for carbon capture and storage, but their tendency to thicken when combined with CO2 limits their efficiency and poses a challenge for their development as a cost-effective alternative to current-generation solutions. Adding alcohol to the mix limits this tendency to thicken in the presence ofmore » CO2 but can also make the liquid more likely to evaporate, which would add significantly to the cost of CO2 capture. To solve this problem, ORNL is developing new classes of ionic liquids with high capacity for absorbing CO2. ORNL’s sponge would reduce the cost associated with the energy that would need to be diverted from power plants to capture CO2 and release it for storage.« less

Criticality in charge-asymmetric hard-sphere ionic fluids.

PubMed

Aqua, Jean-Noël; Banerjee, Shubho; Fisher, Michael E

2005-10-01

Phase separation and criticality are analyzed in z:1 charge-asymmetric ionic fluids of equisized hard spheres by generalizing the Debye-Hückel approach combined with ionic association, cluster solvation by charged ions, and hard-core interactions, following lines developed by Fisher and Levin for the 1:1 case (i.e., the restricted primitive model). Explicit analytical calculations for 2:1 and 3:1 systems account for ionic association into dimers, trimers, and tetramers and subsequent multipolar cluster solvation. The reduced critical temperatures, Tc* (normalized by z), decrease with charge asymmetry, while the critical densities increase rapidly with . The results compare favorably with simulations and represent a distinct improvement over all current theories such as the mean spherical approximation, symmetric Poisson-Boltzmann theory, etc. For z not equal to 1, the interphase Galvani (or absolute electrostatic) potential difference, Deltaphi(T), between coexisting liquid and vapor phases is calculated and found to vanish as absolute value (T-Tc) beta when T-->Tc-with, since our approximations are classical, beta = (1/2). Above Tc, the compressibility maxima and so-called k-inflection loci (which aid the fast and accurate determination of the critical parameters) are found to exhibit a strong z dependence.

Structure and electrical properties of DNA nanotubes embedded in lipid bilayer membranes

PubMed Central

Maiti, Prabal K

2018-01-01

Abstract Engineering the synthetic nanopores through lipid bilayer membrane to access the interior of a cell is a long persisting challenge in biotechnology. Here, we demonstrate the stability and dynamics of a tile-based 6-helix DNA nanotube (DNT) embedded in POPC lipid bilayer using the analysis of 0.2 μs long equilibrium MD simulation trajectories. We observe that the head groups of the lipid molecules close to the lumen cooperatively tilt towards the hydrophilic sugar-phosphate backbone of DNA and form a toroidal structure around the patch of DNT protruding in the membrane. Further, we explore the effect of ionic concentrations to the in-solution structure and stability of the lipid-DNT complex. Transmembrane ionic current measurements for the constant electric field MD simulation provide the I-V characteristics of the water filled DNT lumen in lipid membrane. With increasing salt concentrations, the measured values of transmembrane ionic conductance of the porous DNT lumen vary from 4.3 to 20.6 nS. Simulations of the DNTs with ssDNA and dsDNA overhangs at the mouth of the pore show gating effect with remarkable difference in the transmembrane ionic conductivities for open and close state nanopores. PMID:29136243

Novel Fission-Product Separation based on Room-Temperature Ionic Liquids

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

Rogers, Robin D.

2004-12-31

U.S. DOE's underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive cesium-137 and strontium-90. Because the primary chemical components of alkaline supernatants are sodium nitrate and sodium hydroxide, the majority of this could be disposed of as low level waste if radioactive cesium-137 and strontium- 90 could be selectively removed. The underlying goal of this project was to investigate the application of ionic liquids as novel solvents for new solvent extraction processes for separation of cesium-137 and strontium-90 from tank wastes. Ionic liquids are a distinct sub-set of liquids, comprising only of cationsmore » and anions they are proving to be increasingly interesting fluids for application in systems from electrochemistry to energetic materials, and are also rapidly establishing their promise as viable media for synthesis and separations operations. Properties including low melting points, electrochemical conductivity, wide liquid ranges, lack of vapor-pressure, and chemical tunability have encouraged researchers to explore the uses of ILs in place of volatile organic solvents. The most promising current developments arise from control of the unique combinations of chemical and physical properties characteristic of ionic liquids.« less

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

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

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

DOE PAGES

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue; ...

2018-01-31

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

K-targeted strategy for isolation of phenolic alkaloids of Nelumbo nucifera Gaertn by counter-current chromatography using lysine as a pH regulator.

PubMed

Wang, Yanyan; Zhang, Lihong; Zhou, Hui; Guo, Xiuyun; Wu, Shihua

2017-03-24

Counter-current chromatography (CCC) is an efficient liquid-liquid partition chromatography technique without support matrix. Despite there are many significant advancements in the CCC separation of natural products especially for non-ionic neutral compounds, CCC isolation of ionic compounds including alkaloids is still a challenging process guide by classical partition coefficients (K) or distribution ratio (K C ) because their partition coefficient could not be equal to distribution ratio in common ionic conditions. Here, taking the extract of embryo of the seed of Nelumbo nucifera Gaertn as sample, we introduced a modified K-targeted strategy for isolation of phenolic alkaloids by use of lysine as a pH regulator. The results indicated that if the mass of basic regulators such as aqueous ammonia and lysine added into the solvent system were high enough to inhibit the ionization of the targeted alkaloids, the distribution ratio of targets with ionic and non-ionic molecular forms got stable and might not been changed as the concentration of the pH regulator. In this case, the distribution ratio of target was almost equal to the partition coefficient. Thus, the targets could be isolated by K-targeted CCC separation through adding a certain amount pH regulators into the solvent system. Further experiments also showed that the sample concentration was an important factor on the distribution ratio of targets. Meanwhile, CCC experiments indicated that lysine was more suitable than aqueous ammonia for the separation of phenolic alkaloids because the chemical property of lysine-target complex in the CCC fractions was more stable. Therefore, the preparative CCC separation was performed using 20mM lysine as a pH regulator with more than 800mg injection mass. After simple back-extraction with dichloromethane, the lysine in the CCC fraction was removed completely and pure isoliensinine and neferine were obtained. In summary, the whole results indicated that the modified K-targeted CCC strategy using lysine as the pH regulator was efficient for isolation of phenolic alkaloids from crude plant extracts. It not only provided a practical strategy for the isolation of neferine and its analogues, but also introduced a powerful method to resolve the peak skewing (leading or tailing) in CCC separation of ionic compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Tox-Database.net: a curated resource for data describing chemical triggered in vitro cardiac ion channels inhibition

PubMed Central

2012-01-01

Background Drugs safety issues are now recognized as being factors generating the most reasons for drug withdrawals at various levels of development and at the post-approval stage. Among them cardiotoxicity remains the main reason, despite the substantial effort put into in vitro and in vivo testing, with the main focus put on hERG channel inhibition as the hypothesized surrogate of drug proarrhythmic potency. The large interest in the IKr current has resulted in the development of predictive tools and informative databases describing a drug's susceptibility to interactions with the hERG channel, although there are no similar, publicly available sets of data describing other ionic currents driven by the human cardiomyocyte ionic channels, which are recognized as an overlooked drug safety target. Discussion The aim of this database development and publication was to provide a scientifically useful, easily usable and clearly verifiable set of information describing not only IKr (hERG), but also other human cardiomyocyte specific ionic channels inhibition data (IKs, INa, ICa). Summary The broad range of data (chemical space and in vitro settings) and the easy to use user interface makes tox-database.net a useful tool for interested scientists. Database URL http://tox-database.net. PMID:22947121

Variation in emulsion stabilization behavior of hybrid silicone polymers with change in molecular structure: Phase diagram study.

PubMed

Mehta, Somil C; Somasundaran, P; Kulkarni, Ravi

2009-05-15

Silicone oils are widely used in cosmetics and personal care applications to improve softness and condition skin and hair. Being insoluble in water and most hydrocarbons, a common mode of delivering them is in the form of emulsions. Currently most applications use polyoxyethylene (non-ionic) modified siloxanes as emulsifiers to stabilize silicone oil emulsions. However, ionically grafted silicone polymers have not received much attention. Ionic silicones have significantly different properties than the non-ionic counterpart. Thus considerable potential exists to formulate emulsions of silicones with different water/silicone oil ratios for novel applications. In order to understand the mechanisms underlying the effects of hydrophilic modifications on the ability of hybrid silicone polymers to stabilize various emulsions, this article focuses on the phase diagram studies for silicone emulsions. The emulsifying ability of functional silicones was seen to depend on a number of factors including hydrophilicity of the polymer, nature of the functional groups, the extent of modification, and the method of emulsification. It was observed that the region of stable emulsion in a phase diagram expanded with increase in shear rate. At a given shear rate, the region of stable emulsion and the nature of emulsion (water-in-oil or oil-in-water) was observed to depend on hydrophilic-hydrophobic balance of the hybrid silicone emulsifier. At a fixed amount of modification, the non-ionically modified silicone stabilized an oil-in-water emulsion, whereas the ionic silicones stabilized inverse water-in-oil emulsions. This was attributed to the greater hydrophilicity of the polyoxyethylene modified silicones than the ionic counterparts. In general, it is postulated that with progressive increase in hydrophilicity of hybrid silicone emulsifiers, their tendency to stabilize water-in-oil emulsion decreases with corresponding increase in oil-in-water emulsion. Further, this behavior is hypothesized to depend on the nature of modifying functional groups. Thus a hybrid silicone polymer can be tailored by selecting the nature and degree of hydrophilicity to obtain a desired silicone emulsion.

Prediction of Osmotic Pressure of Ionic Liquids Inside a Nanoslit by MD Simulation and Continuum Approach

NASA Astrophysics Data System (ADS)

Moon, Gi Jong; Yang, Yu Dong; Oh, Jung Min; Kang, In Seok

2017-11-01

Osmotic pressure plays an important role in the processes of charging and discharging of lithium batteries. In this work, osmotic pressure of the ionic liquids confined inside a nanoslit is calculated by using both MD simulation and continuum approach. In the case of MD simulation, an ionic liquid is modeled as singly charged spheres with a short-ranged repulsive Lennard-Jones potential. The radii of the spheres are 0.5nm, reflecting the symmetry of ion sizes for simplicity. The simulation box size is 11nm×11nm×7.5nm with 1050 ion pairs. The concentration of ionic liquid is about 1.922mol/L, and the total charge on an individual wall varies from +/-60e(7.944 μm/cm2) to +/-600e(79.44 μm/cm2) . In the case of continuum approach, we classify the problems according to the correlation length and steric factor, and considered the four separate cases: 1) zero correlation length and zero steric factor, 2) zero correlation length and non-zero steric factor, 3) non-zero correlation length and zero steric factor, and 4) non-zero correlation and non-zero steric factor. Better understanding of the osmotic pressure of ionic liquids confined inside a nanoslit can be achieved by comparing the results of MD simulation and continuum approach. This research was supported by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP: Ministry of Science, ICT & Future Planning) (No. 2017R1D1A1B05035211).

Capturing the effect of [PF3(C2F5)3]-vs. [PF6]-, flexible anion vs. rigid, and scaled charge vs. unit on the transport properties of [bmim]+-based ionic liquids: a comparative MD study.

PubMed

Kowsari, Mohammad H; Ebrahimi, Soraya

2018-05-16

Comprehensive molecular dynamics simulations are performed to study the average single-particle dynamics and the transport properties of 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [bmim][FAP], ionic liquids (ILs) at 400 K. We applied one of the most widely used nonpolarizable all-atom force fields for ILs, both with the original unit (±1) charges on each ion and with the partial charges uniformly scaled to 80-85%, taking into account the average polarizability and tracing the experimentally compatible transport properties. In all simulations, [bmim]+ was considered to be flexible, while the effect of a flexible vs. rigid structure of the anions and the effect of two applied charge sets on the calculated properties were separately investigated in detail. The simulation results showed that replacing [PF6]- with [FAP]-, considering anion flexibility, and applying the charge-scaled model significantly enhanced the ionic self-diffusion, ionic conductivity, inverse viscosity, and hyper anion preference (HAP). Both of the calculated self-diffusion coefficients from the long-time linear slope of the mean-square displacement (MSD) and from the integration of the velocity autocorrelation function (VACF) for the centers of mass of the ions were used for evaluation of the ionic transference number, HAP, ideal Nernst-Einstein ionic conductivity (σNE), and the Stokes-Einstein viscosity. In addition, for quantification of the degree of complicated ionic association (known as the Nernst-Einstein deviation parameter, Δ) and ionicity phenomena in the two studied ILs, the ionic conductivity was determined more rigorously by the Green-Kubo integral of the electric-current autocorrelation function (ECACF), and then the σGK/σNE ratio was evaluated. It was found that the correlated motion of the (cationanion) neighbors in [bmim][FAP] is smaller than in [bmim][PF6]. The relaxation times of the normalized reorientational autocorrelation functions were computed to gain a deep, molecular-level insight into the rotational motion of the ions. The geometric shape of the ion is a key factor in determining its reorientational dynamics. [bmim]+ shows faster translational and slower rotational dynamics in contrast to [PF6]-.

An ionic polymer-metal composite actuator based on PSMI-incorporated PVDF with chemical stability and performance durability

NASA Astrophysics Data System (ADS)

Lu, Jun; Kim, Sang-Gyun; Lee, Sunwoo; Oh, Il-Kwon

2009-07-01

To develop artificial muscles with improved performance, a novel ionic polymer-metal composite (IPMC) actuator was developed by employing the newly-synthesized ionic networking film of poly (styrene-alt-maleimide) (PSMI)- incorporated poly (vinylidene fluoride) (PVDF). Scanning electron microscope and transmission electron microscopy revealed that much smaller and more uniform nano-sized platinum particles were formed on the surfaces of the film as well as within its polymer matrix after the electroless-plating process. Fourier transform infrared results suggested that no hydrolysis occurred for the as-prepared film actuator before and after the exposure to the elevated PH solutions at 25°C for 48h. The new actuator showed much larger tip displacement than that of a Nafion-based counterpart under the applied electrical stimulus, and overcame the back relaxation of the traditional IPMC actuator under the constant voltage. The current actuator was operated over 6.5h at high-frequency sinusoidal excitation, and its tip displacement was still comparable to that of the referenced Nafion actuator when the test was terminated. The excellent electromechanical performance is due to the inherent large ionic-exchange capacity and the unique hydrophilic nano-channels of the ionic networking film. Furthermore, the working principle of the developed IPMC actuator is thought to be based on a combination of piezoelectricity and ionic transport. The film of PSMI-incorporated PVDF has some advantages over the most widely-used Nafion-based one by diversifying niche applications in biomimetic motion, and the present study is believed to open a new avenue for the design and fabrication of the electro-active polymer film with unique functional properties.

Simulation of Ionic Aggregation and Ion Dynamics in Model Ionomers

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie L.

2012-02-01

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. A single-ion conducting polymer electrolyte would be safer and have higher efficiency than the currently-used liquid electrolytes. However, to date ionomeric materials do not have sufficiently high conductivities for practical application. This is most likely because the ions tend to form aggregates, leading to slow ion transport. A key question is therefore how molecular structure affects the ionic aggregation and ion dynamics. To probe these structure-property relationships, we have performed molecular simulations of a set of recently synthesized poly(ethylene-co-acrylic acid) copolymers and ionomers, with a focus on the morphology of the ionic aggregates. The ionomers have a precise, constant spacing of charged groups, making them ideal for direct comparisons with simulations. Ab initio calculations give insight into the expected coordination of cations with fragments of the ionomers. All-atom molecular dynamics (MD) simulations of the ionomer melt show aggregation of the ionic groups into extended string-like clusters. An extensive set of coarse-grained molecular dynamics simulations extend the results to longer times and larger length scales. The structure factors calculated from the MD simulations compare favorably with x-ray scattering data. Furthermore, the simulations give a detailed picture of the sizes, shapes, and composition of the ionic aggregates, and how they depend on polymer architecture. Implications for ion transport will be discussed. [Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.

Mechanically Tunable, Readily Processable Ion Gels by Self-Assembly of Block Copolymers in Ionic Liquids.

PubMed

Lodge, Timothy P; Ueki, Takeshi

2016-01-01

Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.

Hybrid MD-Nernst Planck Model of Alpha-hemolysin Conductance Properties

NASA Technical Reports Server (NTRS)

Cozmuta, Ioana; O'Keefer, James T.; Bose, Deepak; Stolc, Viktor

2006-01-01

Motivated by experiments in which an applied electric field translocates polynucleotides through an alpha-hemolysin protein channel causing ionic current transient blockade, a hybrid simulation model is proposed to predict the conductance properties of the open channel. Time scales corresponding to ion permeation processes are reached using the Poisson-Nemst-Planck (PNP) electro-diffusion model in which both solvent and local ion concentrations are represented as a continuum. The diffusion coefficients of the ions (K(+) and Cl(-)) input in the PNP model are, however, calculated from all-atom molecular dynamics (MD). In the MD simulations, a reduced representation of the channel is used. The channel is solvated in a 1 M KCI solution, and an external electric field is applied. The pore specific diffusion coefficients for both ionic species are reduced 5-7 times in comparison to bulk values. Significant statistical variations (17-45%) of the pore-ions diffusivities are observed. Within the statistics, the ionic diffusivities remain invariable for a range of external applied voltages between 30 and 240mV. In the 2D-PNP calculations, the pore stem is approximated by a smooth cylinder of radius approx. 9A with two constriction blocks where the radius is reduced to approx. 6A. The electrostatic potential includes the contribution from the atomistic charges. The MD-PNP model shows that the atomic charges are responsible for the rectifying behaviour and for the slight anion selectivity of the a-hemolysin pore. Independent of the hierarchy between the anion and cation diffusivities, the anionic contribution to the total ionic current will dominate. The predictions of the MD-PNP model are in good agreement with experimental data and give confidence in the present approach of bridging time scales by combining a microscopic and macroscopic model.

A self-consistent model of ionic wind generation by negative corona discharges in air with experimental validation

NASA Astrophysics Data System (ADS)

Chen, She; Nobelen, J. C. P. Y.; Nijdam, S.

2017-09-01

Ionic wind is produced by a corona discharge when gaseous ions are accelerated in the electric field and transfer their momentum to neutral molecules by collisions. This technique is promising because a gas flow can be generated without the need for moving parts and can be easily miniaturized. The basic theory of ionic wind sounds simple but the details are far from clear. In our experiment, a negative DC voltage is applied to a needle-cylinder electrode geometry. Hot wire anemometry is used to measure the flow velocity at the downstream exit of the cylinder. The flow velocity fluctuates but the average velocity increases with the voltage. The current consists of a regular train of pulses with short rise time, the well-known Trichel pulses. To reveal the ionic wind mechanism in the Trichel pulse stage, a three-species corona model coupled with gas dynamics is built. The drift-diffusion equations of the plasma together with the Navier-Stokes equations of the flow are solved in COMSOL Multiphysics. The electric field, net number density of charged species, electrohydrodynamic (EHD) body force and flow velocity are calculated in detail by a self-consistent model. Multiple time scales are employed: hundreds of microseconds for the plasma characteristics and longer time scales (˜1 s) for the flow behavior. We found that the flow velocity as well as the EHD body force have opposite directions in the ionization region close to the tip and the ion drift region further away from the tip. The calculated mean current, Trichel pulse frequency and flow velocity are very close to our experimental results. Furthermore, in our simulations we were able to reproduce the mushroom-like minijets observed in experiments.

Role of bundle helices in a regulatory crosstalk in the trimeric betaine transporter BetP.

PubMed

Gärtner, Rebecca M; Perez, Camilo; Koshy, Caroline; Ziegler, Christine

2011-12-02

The Na(+)-coupled betaine symporter BetP regulates transport activity in response to hyperosmotic stress only in its trimeric state, suggesting a regulatory crosstalk between individual protomers. BetP shares the overall fold of two inverted structurally related five-transmembrane (TM) helix repeats with the sequence-unrelated Na(+)-coupled symporters LeuT, vSGLT, and Mhp1, which are neither trimeric nor regulated in transport activity. Conformational changes characteristic for this transporter fold involve the two first helices of each repeat, which form a four-TM-helix bundle. Here, we identify two ionic networks in BetP located on both sides of the membrane that might be responsible for BetP's unique regulatory behavior by restricting the conformational flexibility of the four-TM-helix bundle. The cytoplasmic ionic interaction network links both first helices of each repeat in one protomer to the osmosensing C-terminal domain of the adjacent protomer. Moreover, the periplasmic ionic interaction network conformationally locks the four-TM-helix bundle between the same neighbor protomers. By a combination of site-directed mutagenesis, cross-linking, and betaine uptake measurements, we demonstrate how conformational changes in individual bundle helices are transduced to the entire bundle by specific inter-helical interactions. We suggest that one purpose of bundle networking is to assist crosstalk between protomers during transport regulation by specifically modulating the transition from outward-facing to inward-facing state. Copyright © 2011 Elsevier Ltd. All rights reserved.

Arrays of microscopic organic LEDs for high-resolution optogenetics

PubMed Central

Steude, Anja; Witts, Emily C.; Miles, Gareth B.; Gather, Malte C.

2016-01-01

Optogenetics is a paradigm-changing new method to study and manipulate the behavior of cells with light. Following major advances of the used genetic constructs over the last decade, the light sources required for optogenetic control are now receiving increased attention. We report a novel optogenetic illumination platform based on high-density arrays of microscopic organic light-emitting diodes (OLEDs). Because of the small dimensions of each array element (6 × 9 μm2) and the use of ultrathin device encapsulation, these arrays enable illumination of cells with unprecedented spatiotemporal resolution. We show that adherent eukaryotic cells readily proliferate on these arrays, and we demonstrate specific light-induced control of the ionic current across the membrane of individual live cells expressing different optogenetic constructs. Our work paves the way for the use of OLEDs for cell-specific optogenetic control in cultured neuronal networks and for acute brain slices, or as implants in vivo. PMID:27386540

Improved cost-effective fabrication of arbitrarily shaped μIPMC transducers

NASA Astrophysics Data System (ADS)

Feng, Guo-Hua; Chen, Ri-Hong

2008-01-01

Conventional ionic polymer-metal composite (IPMC) production cuts individual transducers from bulk IPMC sheets. This paper presents a novel photolithographic technique that grows a large array of identical devices on a thin (~µm range) parylene diaphragm supported on a perforated substrate of material that is immune to the subsequent processing liquids. In particular, the new technique relies on a unique wax fill-up and removal concept that can produce arbitrarily shaped Nafion films with micron feature size. The developed process is cheap and results in devices of high uniformity and reliability, with greater design flexibility. Microtensile testing characterizes the fracture profiles of the non-electroded Nafion film and IPMC. Young's modulus is characterized, as well as maximum displacement and current consumption under various loading, driving voltages, waveforms and frequencies. High product quality and low process costs make this process of interest for mass production of micromachined IPMC transducers.

Extending the diffuse layer model of surface acidity behavior: I. Model development

EPA Science Inventory

Considerable disenchantment exists within the environmental research community concerning our current ability to accurately model surface-complexation-mediated low-porewater-concentration ionic contaminant partitioning with natural surfaces. Several authors attribute this unaccep...

Neuronal networks: flip-flops in the brain.

PubMed

McCormick, David A

2005-04-26

Neuronal activity can rapidly flip-flop between stable states. Although these semi-stable states can be generated through interactions of neuronal networks, it is now known that they can also occur in vivo through intrinsic ionic currents.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore

PubMed Central

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2017-01-01

A stable nanoscale thermal hot spot, with temperature approaching 100 °C, is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z, collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte. PMID:27715110

A temperature, pH and sugar triple-stimuli-responsive nanofluidic diode.

PubMed

Zheng, Yu-Bin; Zhao, Shuang; Cao, Shuo-Hui; Cai, Sheng-Lin; Cai, Xiu-Hong; Li, Yao-Qun

2017-01-07

In this article, we have demonstrated for the first time a triple stimuli-responsive nanofluidic diode that can rectify ionic current under multiple external stimuli including temperature, pH, and sugar. This diode was fabricated by immobilizing poly[2-(dimethylamino)ethyl methacrylate]-co-[4-vinyl phenylboronic acid] (P(DMAEMA-co-VPBA)) onto the wall of a single glass conical nanopore channel via surface-initiator atom transfer radical polymerization (SI-ATRP). The copolymer brushes contain functional groups sensitive to pH, temperature and sugar that can induce charge and configuration change to affect the status of the pore wall. The experimental results confirmed that the P(DMAEMA-co-VPBA) brush modified nanochannel regulated the ionic current rectification successfully under three different external stimuli. This biomimetically inspired research simulates the complex biological multi-functions of ion channels and promotes the development of "smart" biomimetic nanochannel systems for actuating and sensing applications.

Membrane currents in the oocyte of the toad Bufo arenarum.

PubMed

Kotsias, Basilio A; Damiano, Alicia E; Godoy, Sebastian; Assef, Yanina; Ibarra, Cristina; Cantiello, Horacio F

2002-03-01

The amphibian oocyte cell model is widely used for heterologous expression of ionic channels and receptors. Little is known, however, about the physiology of oocyte cell models other than Xenopus laevis. In this study, the two-electrode voltage clamp technique was used to assess the most common electrical patterns of oocytes of the South American toad Bufo arenarum. Basal membrane resistance, resting potential, and ionic currents were determined in this cell model. The oocyte transmembrane resistance was 0.35 M(Omega), and the resting potential in normal saline was about -33 mV with a range between -20 mV and -50 mV. This is, to our knowledge, the first attempt to begin an understanding of the ion transport mechanisms of Bufo arenarum oocytes. This cell model may provide a viable alternative to the expression of ion channels, in particular those endogenously observed in Xenopus laevis oocytes. Copyright 2002 Wiley-Liss, Inc.

Electrostatic Debye layer formed at a plasma-liquid interface

NASA Astrophysics Data System (ADS)

Rumbach, Paul; Clarke, Jean Pierre; Go, David B.

2017-05-01

We construct an analytic model for the electrostatic Debye layer formed at a plasma-liquid interface by combining the Gouy-Chapman theory for the liquid with a simple parabolic band model for the plasma sheath. The model predicts a nonlinear scaling between the plasma current density and the solution ionic strength, and we confirmed this behavior with measurements using a liquid-anode plasma. Plots of the measured current density as a function of ionic strength collapse the data and curve fits yield a plasma electron density of ˜1019m-3 and an electric field of ˜104V /m on the liquid side of the interface. Because our theory is based firmly on fundamental physics, we believe it can be widely applied to many emerging technologies involving the interaction of low-temperature, nonequilibrium plasma with aqueous media, including plasma medicine and various plasma chemical synthesis techniques.

An experimental and numerical approach to understand the effect of the IPMC composition on its sensing and energy harvesting behavior

NASA Astrophysics Data System (ADS)

Akle, Barbar; Khairallah, Reef; Challita, Elio

2014-03-01

Ionic Polymer Metal Composite (IPMC) is an Electo-Active Polymer (EAP) that is well-known for its actuation and sensing behavior. It has been shown that in charge sensing mode an IPMC generates one order of magnitude larger current as compared to piezoelectric materials. However the voltage generated is on the order of couple millivolts, making it less attractive as a sensor and energy harvester. Previous numerical work by the author, demonstrated that increasing the ionic concentration of the ionomer will increase the current and voltage generated by an IPMC. Conversely, the previous study showed that the electrode composition and architecture had minimal effects. This paper will present an experimental investigation of the effect of changing the composition of the ionomer, the membrane thickness, and electrode architecture on the sensing and energy harvesting behavior. The response of all IPMC transducers is analyzed and compared to numerical simulations.

Simultaneous Scanning Ion Conductance Microscopy and Atomic Force Microscopy with Microchanneled Cantilevers

NASA Astrophysics Data System (ADS)

Ossola, Dario; Dorwling-Carter, Livie; Dermutz, Harald; Behr, Pascal; Vörös, János; Zambelli, Tomaso

2015-12-01

We combined scanning ion conductance microscopy (SICM) and atomic force microscopy (AFM) into a single tool using AFM cantilevers with an embedded microchannel flowing into the nanosized aperture at the apex of the hollow pyramid. An electrode was positioned in the AFM fluidic circuit connected to a second electrode in the bath. We could thus simultaneously measure the ionic current and the cantilever bending (in optical beam deflection mode). First, we quantitatively compared the SICM and AFM contact points on the approach curves. Second, we estimated where the probe in SICM mode touches the sample during scanning on a calibration grid and applied the finding to image a network of neurites on a Petri dish. Finally, we assessed the feasibility of a double controller using both the ionic current and the deflection as input signals of the piezofeedback. The experimental data were rationalized in the framework of finite elements simulations.

Sensitivity of Rabbit Ventricular Action Potential and Ca2+ Dynamics to Small Variations in Membrane Currents and Ion Diffusion Coefficients

PubMed Central

Lo, Yuan Hung; Peachey, Tom; Abramson, David; McCulloch, Andrew

2013-01-01

Little is known about how small variations in ionic currents and Ca2+ and Na+ diffusion coefficients impact action potential and Ca2+ dynamics in rabbit ventricular myocytes. We applied sensitivity analysis to quantify the sensitivity of Shannon et al. model (Biophys. J., 2004) to 5%–10% changes in currents conductance, channels distribution, and ion diffusion in rabbit ventricular cells. We found that action potential duration and Ca2+ peaks are highly sensitive to 10% increase in L-type Ca2+ current; moderately influenced by 10% increase in Na+-Ca2+ exchanger, Na+-K+ pump, rapid delayed and slow transient outward K+ currents, and Cl− background current; insensitive to 10% increases in all other ionic currents and sarcoplasmic reticulum Ca2+ fluxes. Cell electrical activity is strongly affected by 5% shift of L-type Ca2+ channels and Na+-Ca2+ exchanger in between junctional and submembrane spaces while Ca2+-activated Cl−-channel redistribution has the modest effect. Small changes in submembrane and cytosolic diffusion coefficients for Ca2+, but not in Na+ transfer, may alter notably myocyte contraction. Our studies highlight the need for more precise measurements and further extending and testing of the Shannon et al. model. Our results demonstrate usefulness of sensitivity analysis to identify specific knowledge gaps and controversies related to ventricular cell electrophysiology and Ca2+ signaling. PMID:24222910

Development of an ionic-liquid-based dispersive liquid-liquid microextraction method for the determination of antichagasic drugs in human breast milk: Optimization by central composite design.

PubMed

Padró, Juan M; Pellegrino Vidal, Rocío B; Echevarria, Romina N; Califano, Alicia N; Reta, Mario R

2015-05-01

Chagas disease constitutes a major public health problem in Latin America. Human breast milk is a biological sample of great importance for the analysis of therapeutic drugs, as unwanted exposure through breast milk could result in pharmacological effects in the nursing infant. Thus, the goal of breast milk drug analysis is to inquire to which extent a neonate may be exposed to a drug during lactation. In this work, we developed an analytical technique to quantify benznidazole and nifurtimox (the two antichagasic drugs currently available for medical treatment) in human breast milk, with a simple sample pretreatment followed by an ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography and UV detection. For this technique, the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate has been used as the "extraction solvent." A central composite design was used to find the optimum values for the significant variables affecting the extraction process: volume of ionic liquid, volume of dispersant solvent, ionic strength, and pH. At the optimum working conditions, the average recoveries were 77.5 and 89.7%, the limits of detection were 0.06 and 0.09 μg/mL and the interday reproducibilities were 6.25 and 5.77% for benznidazole and nifurtimox, respectively. The proposed methodology can be considered sensitive, simple, robust, accurate, and green. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of Cleanliness Test Methods for Spacecraft PCB Assemblies

NASA Astrophysics Data System (ADS)

Tegehall, P.-E.; Dunn, B. D.

2006-10-01

Ionic contamination on printed-circuit-board assemblies may cause current leakage and short-circuits. The present cleanliness requirement in ECSS-Q-70-08, "The manual soldering of high-reliability electrical connections", is that the ionic contamination shall be less than 1.56 fl-glcm2 NaCI equivalents. The relevance of the method used for measurement of the ionic contamination level, resistivity of solvent extract, has been questioned. Alternative methods are ion chromatography and measurement of surface insulation resistance, but these methods also have their drawbacks. These methods are first described and their advantages and drawbacks are discussed. This is followed by an experimental evaluation of the three methods. This was done by soldering test vehicles at four manufacturers of space electronics using their ordinary processes for soldering and cleaning printed board assemblies. The experimental evaluation showed that the ionic contamination added by the four assemblers was very small and well below the acceptance criterion in ECSS-Q-70-80. Ion-chromatography analysis showed that most of the ionic contamination on the cleaned assembled boards originated from the hot-oil fusing of the printed circuit boards. Also, the surface insulation resistance was higher on the assembled boards compared to the bare printed circuit boards. Since strongly activated fluxes are normally used when printed circuit boards are hot-oil fused, it is essential that they are thoroughly cleaned in order to achieve low contamination levels on the final printed-board assemblies.

Design and synthesis of magnetic nanoparticles with gold shells for single particle optical tracking

NASA Astrophysics Data System (ADS)

Lim, Jitkang

The design, synthesis, and characterization of iron oxide core, gold shell nanoparticles are studied in this thesis. Firstly, nanoparticles with 18 +/- 1.7 nm diameter iron oxide cores with ˜5 nm thick gold shells were synthesized via a new seed-mediated electroless deposition method. The nanoparticles were superparamagnetic at room temperature and could be reversibly collected by a permanent magnet. These nanoparticles displayed a sharp localized surface plasmon resonance peak at 605 nm, as predicted by scattering theory, and their large scattering cross-section allowed them to be individually resolved in darkfield optical microscopy while undergoing Brownian motion in aqueous suspension. Later, commercially available 38 +/- 3.8 nm diameter spherical iron oxide nanoparticles (from Ocean Nanotech, Inc) were employed to make core-shell particles. These particles were decorated with cationic poly(diallyldimethylammonium chloride) (PDDA) which further promotes the attachment of small gold clusters. After gold seeding, the average hydrodynamic diameter of the core-shell particles is 172 +/- 65.9 nm. The magnetophoretic motion of these particles was guided by a piece of magnetized mu-metal. Individual particle trajectories were observed by darkfield optical microscopy. The typical magnetophoretic velocity achieved was within the range of 1--10 mum/sec. Random walk analysis performed on these particles while undergoing Brownian motion confirmed that individual particles were indeed being imaged. The particle size variation within the observed sample obtained through random walk analysis was within the size distribution obtained by dynamic light scattering. When the current to the solenoid used to magnetize the mu-metal was turned off, all the collected core-shell particles were readily redispersed by diffusion back into the surrounding environment. A Peclet number analysis was performed to probe the convective motion of nanospheres and nanorods under the influence of magnetophoresis and diffusion. Under most circumstances, magnetophoretic behavior dominates diffusion for nanorods, as the magnetic field lines tend to align the magnetic moment along the rod axis. The synthesis and dispersion of fluorophore-tagged nanorods are described. Fluorescence microscopy was employed to image the nanorod motion in a magnetic field gradient. The preliminary experimental data are consistent with the Peclet number analysis. Lastly, the colloidal stability of iron oxide core, gold shell nanoparticles in high ionic strength media was investigated. Such particles are sufficiently charged to be stable against flocculation without modification in low ionic strength media, but they require surface modification to be stably dispersed in elevated ionic strength media that are appropriate for biotechnological applications. Dynamic light scattering and ultraviolet-visible spectrophotometry were used to monitor the colloidal stability of core-shell particles in pH 7.4, 150 mM ionic strength phosphate buffered saline (PBS). While uncoated particles flocculated immediately upon being introduced into PBS, core-shell particles with adsorbed layers of bovine serum albumin or the amphiphilic triblock copolymers Pluronic F127 and Pluronic F68 resist flocculation after more than five days in PBS. Adsorbed dextran allowed flocculation that was limited to the formation of small clusters, while poly(ethylene glycol) homopolymers ranging in molecular weight from 6,000 to 100,000 were ineffective steric stabilizers. The effectiveness of adsorbed Pluronic copolymers as steric stabilizers was interpreted in terms of the measured adsorbed layer thickness and extended DLVO theory predictions of the interparticle interactions.

Polarity governed selective amplification of through plane proton shuttling in proton exchange membrane fuel cells.

PubMed

Gautam, Manu; Chattanahalli Devendrachari, Mruthyunjayachari; Thimmappa, Ravikumar; Raja Kottaichamy, Alagar; Pottachola Shafi, Shahid; Gaikwad, Pramod; Makri Nimbegondi Kotresh, Harish; Ottakam Thotiyl, Musthafa

2017-03-15

Graphene oxide (GO) anisotropically conducts protons with directional dominance of in plane ionic transport (σ IP) over the through plane (σ TP). In a typical H 2 -O 2 fuel cell, since the proton conduction occurs through the plane during its generation at the fuel electrode, it is indeed inevitable to selectively accelerate GO's σ TP for advancement towards a potential fuel cell membrane. We successfully achieved ∼7 times selective amplification of GO's σ TP by tuning the polarity of the dopant molecule in its nanoporous matrix. The coexistence of strongly non-polar and polar domains in the dopant demonstrated a synergistic effect towards σ TP with the former decreasing the number of water molecules coordinated to protons by ∼3 times, diminishing the effects of electroosmotic drag exerted on ionic movements, and the latter selectively accelerating σ TP across the catalytic layers by bridging the individual GO planes via extensive host guest H-bonding interactions. When they are decoupled, the dopant with mainly non-polar or polar features only marginally enhances the σ TP, revealing that polarity factors contribute to fuel cell relevant transport properties of GO membranes only when they coexist. Fuel cell polarization and kinetic analyses revealed that these multitask dopants increased the fuel cell performance metrics of the power and current densities by ∼3 times compared to the pure GO membranes, suggesting that the functional group factors of the dopants are of utmost importance in GO-based proton exchange membrane fuel cells.

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

Simultaneous Interfacial Reactivity and Topography Mapping with Scanning Ion Conductance Microscopy.

PubMed

Momotenko, Dmitry; McKelvey, Kim; Kang, Minkyung; Meloni, Gabriel N; Unwin, Patrick R

2016-03-01

Scanning ion conductance microscopy (SICM) is a powerful technique for imaging the topography of a wide range of materials and interfaces. In this report, we develop the use and scope of SICM, showing how it can be used for mapping spatial distributions of ionic fluxes due to (electro)chemical reactions occurring at interfaces. The basic idea is that there is a change of ion conductance inside a nanopipet probe when it approaches an active site, where the ionic composition is different to that in bulk solution, and this can be sensed via the current flow in the nanopipet with an applied bias. Careful tuning of the tip potential allows the current response to be sensitive to either topography or activity, if desired. Furthermore, the use of a distance modulation SICM scheme allows reasonably faithful probe positioning using the resulting ac response, irrespective of whether there is a reaction at the interface that changes the local ionic composition. Both strategies (distance modulation or tuned bias) allow simultaneous topography-activity mapping with a single channel probe. The application of SICM reaction imaging is demonstrated on several examples, including voltammetric mapping of electrocatalytic reactions on electrodes and high-speed electrochemical imaging at rates approaching 4 s per image frame. These two distinct approaches provide movies of electrochemical current as a function of potential with hundreds of frames (images) of surface reactivity, to reveal a wealth of spatially resolved information on potential- (and time) dependent electrochemical phenomena. The experimental studies are supported by detailed finite element method modeling that places the technique on a quantitative footing.

Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

PubMed

Oldiges, K; Diddens, D; Ebrahiminia, M; Hooper, J B; Cekic-Laskovic, I; Heuer, A; Bedrov, D; Winter, M; Brunklaus, G

2018-06-20

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

Non-aqueous aluminium-air battery based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Revel, Renaud; Audichon, Thomas; Gonzalez, Serge

2014-12-01

A promising metal-air secondary battery based on aluminium-oxygen couple is described. In this paper, we observed that an aluminium-air battery employing EMImCl, AlCl3 room temperature ionic liquid (RTIL) as electrolyte and aluminium as negative electrode, has an exceptional reduced self-discharged rate. Due to its new and innovative type of electrolyte, this aluminium-air battery can support relatively high current densities (up to 0.6 mA cm-2) and an average voltage of 0.6-0.8 V. Such batteries may find immediate applications, as they can provide an internal, built-in autonomous and self-sustained energy source.

Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control

USGS Publications Warehouse

Morgan, J.W.; Wandless, G.A.

1980-01-01

Rare earth element (REE) abundances were measured by neutron activation analysis in anhydrite (CaSO4), barite (BaSO4), siderite (FeCO3) and galena (PbS). A simple crystal-chemical model qualitatively describes the relative affinities for REE substitution in anhydrite, barite, and siderite. When normalized to 'crustal' abundances (as an approximation to the hydrothermal fluid REE pattern), log REE abundance is a surprisingly linear function of (ionic radius of major cation-ionic radius of REE)2 for the three hydrothermal minerals, individually and collectively. An important exception, however, is Eu, which is anomalously enriched in barite and depleted in siderite relative to REE of neighboring atomic number and trivalent ionic radius. In principle, REE analyses of suitable pairs of co-existing hydrothermal minerals, combined with appropriate experimental data, could yield both the REE content and the temperature of the parental hydrothermal fluid. The REE have only very weak chalcophilic tendencies, and this is reflected by the very low abundances in galena-La, 0.6 ppb; Sm, 0.06 ppb; the remainder are below detection limits. ?? 1980.

Effects of Environmental Stresses and in Vitro Digestion on the Release of Tocotrienols Encapsulated Within Chitosan-Alginate Microcapsules.

PubMed

Tan, Phui Yee; Tan, Tai Boon; Chang, Hon Weng; Tey, Beng Ti; Chan, Eng Seng; Lai, Oi Ming; Sham Baharin, Badlishah; Nehdi, Imededdine Arbi; Tan, Chin Ping

2017-12-06

Considering the health benefits of tocotrienols, continuous works have been done on the encapsulation and delivery of these compounds. In this study, we encapsulated tocotrienols in chitosan-alginate microcapsules and evaluated their release profile. Generally, these tocotrienols microcapsules (TM) displayed high thermal stability. When subjected to pH adjustments (pH 1-9), we observed that the release of tocotrienols was the highest (33.78 ± 0.18%) under basic conditions. The TM were also unstable against the effect of ionic strength, with a high release (70.73 ± 0.04%) of tocotrienols even at a low sodium chloride concentration (50 mM). As for the individual isomers, δ-tocotrienol was the most sensitive to pH and ionic strength. In contrast, β-/γ-tocotrienols were the most ionic-stable isomers but more responsive toward thermal treatment. Simulated gastrointestinal model showed that the chitosan-alginate-based TM could be used to retain tocotrienols in the gastric and subsequently release them in the intestines for possible absorption.

Ionic solutions of two-dimensional materials

NASA Astrophysics Data System (ADS)

Cullen, Patrick L.; Cox, Kathleen M.; Bin Subhan, Mohammed K.; Picco, Loren; Payton, Oliver D.; Buckley, David J.; Miller, Thomas S.; Hodge, Stephen A.; Skipper, Neal T.; Tileli, Vasiliki; Howard, Christopher A.

2017-03-01

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

Determination of ionic species formed during growth of Escherichia coli by capillary isotachophoresis.

PubMed

Futschik, K; Ammann, M; Bachmayer, S; Kenndler, E

1993-08-06

The ionic species that are formed during the microbial growth of Escherichia coli were determined by capillary isotachophoresis as a function of the time of cultivation. This formation was indicated by the change in a sum parameter, the impedance of the nutrient broth, measured by a special electrode system. Based on the determination of the individual ions formed under the given conditions (identified as acetate, lactate, alpha-ketoglutarate, fumarate, ammonium and probably a simple amine), the change in conductivity was calculated and compared with that obtained by the impedance measurement of the bulk medium. From the results it can be concluded that the change in the sum parameter as a function of time is originated by the ions determined.

Determination of successive complexation constants in an ionic liquid: complexation of UO(2)(2+) with NO(3)(-) in C(4)-mimTf(2)N studied by UV-Vis spectroscopy.

PubMed

Georg, Sylvia; Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde; Petitjean, Laetitia; Picquet, Michel; Solov'ev, Vitaly

2010-04-01

The complexation of UO(2)(2+) with NO(3)(-) has been investigated in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by UV-vis spectroscopy at T = 18.5 degrees C. The complexation is evidenced through the appearance of four peaks at 425, 438, 453, and 467 nm. EXAFS data indicate that the trinitrato complex, UO(2)(NO(3))(3)(-), is dominating the speciation for a reagent ratio of [NO(3)(-)]/[UO(2)(2+)] > 3. Assuming three successive complexation steps, the conditional stability constants are calculated, the individual absorption spectra are derived, and a speciation plot is presented.

Boosting current generation in microbial fuel cells by an order of magnitude by coating an ionic liquid polymer on carbon anodes.

PubMed

Yang, Lu; Deng, Wenfang; Zhang, Youming; Tan, Yueming; Ma, Ming; Xie, Qingji

2017-05-15

Microbial fuel cells (MFCs) have attracted great attentions due to their great application potentials, but the relatively low power densities of MFCs still hinder their widespread practical applications. Herein, we report that the current generation in MFCs can be boosted by an order of magnitude, simply by coating a hydrophilic and positively charged ionic liquid polymer (ILP) on carbon cloth (CC) or carbon felt (CF). The ILP coating not only can increase the bacterial loading capacity due to the electrostatic interactions between ILP and bacterial cells, but also can improve the mediated extracellular electron transfer between the electrode and the cytochrome proteins on the outer membrane of Shewanella putrefaciens cells. As a result, the maximum power density of a MFC equipped with the CF-ILP bioanode is as high as 4400±170mWm -2 , which is amongst the highest values reported to date. This work demonstrates a new strategy for greatly boosting the current generation in MFCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanowire-nanopore transistor sensor for DNA detection during translocation

NASA Astrophysics Data System (ADS)

Xie, Ping; Xiong, Qihua; Fang, Ying; Qing, Quan; Lieber, Charles

2011-03-01

Nanopore sequencing, as a promising low cost, high throughput sequencing technique, has been proposed more than a decade ago. Due to the incompatibility between small ionic current signal and fast translocation speed and the technical difficulties on large scale integration of nanopore for direct ionic current sequencing, alternative methods rely on integrated DNA sensors have been proposed, such as using capacitive coupling or tunnelling current etc. But none of them have been experimentally demonstrated yet. Here we show that for the first time an amplified sensor signal has been experimentally recorded from a nanowire-nanopore field effect transistor sensor during DNA translocation. Independent multi-channel recording was also demonstrated for the first time. Our results suggest that the signal is from highly localized potential change caused by DNA translocation in none-balanced buffer condition. Given this method may produce larger signal for smaller nanopores, we hope our experiment can be a starting point for a new generation of nanopore sequencing devices with larger signal, higher bandwidth and large-scale multiplexing capability and finally realize the ultimate goal of low cost high throughput sequencing.

Presynaptic membrane potential affects transmitter release in an identified neuron in Aplysia by modulating the Ca2+ and K+ currents.

PubMed

Shapiro, E; Castellucci, V F; Kandel, E R

1980-01-01

We have examined the relationships between the modulation of transmitter release and of specific ionic currents by membrane potential in the cholinergic interneuron L10 of the abdominal ganglion of Aplysia californica. The presynaptic cell body was voltage-clamped under various pharmacological conditions and transmitter release from the terminals was assayed simultaneously by recording the synaptic potentials in the postsynaptic cell. When cell L10 was voltage-clamped from a holding potential of -60 mV in the presence of tetrodotoxin, graded transmitter release was evoked by depolarizing command pulses in the membrane voltage range (-35 mV to + 10 mV) in which the Ca(2+) current was also increasing. Depolarizing the holding potential of L10 results in increased transmitter output. Two ionic mechanisms contribute to this form of plasticity. First, depolarization inactivates some K(+) channels so that depolarizing command pulses recruit a smaller K(+) current. In unclamped cells the decreased K(+) conductance causes spike-broadening and increased influx of Ca(2+) during each spike. Second, small depolarizations around resting potential (-55 mV to -35 mV) activate a steady-state Ca(2+) current that also contributes to the modulation of transmitter release, because, even with most presynaptic K(+) currents blocked pharmacologically, depolarizing the holding potential still increases transmitter release. In contrast to the steady-state Ca(2+) current, the transient inward Ca(2+) current evoked by depolarizing clamp steps is relatively unchanged from various holding potentials.

Temporal differentiation of pH-dependent capacitive current from dopamine.

PubMed

Yoshimi, Kenji; Weitemier, Adam

2014-09-02

Voltammetric recording of dopamine (DA) with fast-scan cyclic voltammetry (FSCV) on carbon fiber microelectrodes have been widely used, because of its high sensitivity to dopamine. However, since an electric double layer on a carbon fiber surface in a physiological ionic solution behaves as a capacitor, fast voltage manipulation in FSCV induces large capacitive current. The faradic current from oxidation/reduction of target chemicals must be extracted from this large background current. It is known that ionic shifts, including H(+), influence this capacitance, and pH shift can cause confounding influences on the FSCV recordings within a wide range of voltage. Besides FSCV with a triangular waveform, we have been using rectangular pulse voltammetry (RPV) for dopamine detection in the brain. In this method, the onset of a single pulse causes a large capacitive current, but unlike FSCV, the capacitive current is restricted to a narrow temporal window of just after pulse onset (<5 ms). In contrast, the peak of faradic current from dopamine oxidation occurs after a delay of more than a few milliseconds. Taking advantage of the temporal difference, we show that RPV could distinguish dopamine from pH shifts clearly and easily. In addition, the early onset current was useful to evaluate pH shifts. The narrow voltage window of our RPV pulse allowed a clear differentiation of dopamine and serotonin (5-HT), as we have shown previously. Additional recording with RPV, alongside FSCV, would improve identification of chemicals such as dopamine, pH, and 5-HT.

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

Nanoscale lubrication of ionic surfaces controlled via a strong electric field

DOE PAGES

Strelcov, Evgheni; Bocharova, Vera; Sumpter, Bobby G.; ...

2015-01-27

Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip andmore » salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. Lastly, the demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.« less

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

Crew Exploration Vehicle Potable Water System Verification Description

NASA Technical Reports Server (NTRS)

Tuan, George; Peterson, Laurie J.; Vega, Leticia M.

2010-01-01

A stored water system on the crew exploration vehicle (CEV) will supply the crew with potable water for: drinking and food rehydration, hygiene, medical needs, sublimation, and various contingency situations. The current baseline biocide for the stored water system is ionic silver, similar in composition to the biocide used to maintain the quality of the water, transferred from the orbiter to the International Space Station, stored in contingency water containers. In the CEV water system, a depletion of the ionic silver biocide is expected due to ionic silver-plating onto the surfaces of materials within the CEV water system, thus negating its effectiveness as a biocide. Because this may be the first time NASA is considering a stored water system for long-term missions that do not maintain a residual biocide, a team of experts in materials compatibility, biofilms and point-of-use filters, surface treatment and coatings, and biocides has been created to pinpoint concerns and perform the testing that will help alleviate concerns related to the CEV water system.

Improved in situ saccharification of cellulose pretreated by dimethyl sulfoxide/ionic liquid using cellulase from a newly isolated Paenibacillus sp. LLZ1.

PubMed

Hu, Dongxue; Ju, Xin; Li, Liangzhi; Hu, Cuiying; Yan, Lishi; Wu, Tianyun; Fu, Jiaolong; Qin, Ming

2016-02-01

A cellulase producing strain was newly isolated from soil samples and identified as Paenibacillus sp. LLZ1. A novel aqueous-dimethyl sulfoxide (DMSO)/1-ethyl-3-methylimidazolium diethyl phosphate ([Emin]DEP)-cellulase system was designed and optimized. In the pretreatment, DMSO was found to be a low-cost substitute of up to 70% ionic liquid to enhance the cellulose dissolution. In the enzymatic saccharification, the optimum pH and temperature of the Paenibacillus sp. LLZ1 cellulase were identified as 6.0 and 40°C, respectively. Under the optimized reaction condition, the conversion of microcrystalline cellulose and bagasse cellulose increased by 39.3% and 37.6%, compared with unpretreated cellulose. Compared to current methods of saccharification, this new approach has several advantages including lower operating temperature, milder pH, and less usage of ionic liquid, indicating a marked progress in environmental friendly hydrolysis of biomass-based materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Wang, Hui; Chen, Yan; Hood, Zachary D.

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Chronic Effect of Aspartame on Ionic Homeostasis and Monoamine Neurotransmitters in the Rat Brain.

PubMed

Abhilash, M; Alex, Manju; Mathews, Varghese V; Nair, R Harikumaran

2014-07-01

Aspartame is one of the most widely used artificial sweeteners globally. Data concerning acute neurotoxicity of aspartame is controversial, and knowledge on its chronic effect is limited. In the current study, we investigated the chronic effects of aspartame on ionic homeostasis and regional monoamine neurotransmitter concentrations in the brain. Our results showed that aspartame at high dose caused a disturbance in ionic homeostasis and induced apoptosis in the brain. We also investigated the effects of aspartame on brain regional monoamine synthesis, and the results revealed that there was a significant decrease of dopamine in corpus striatum and cerebral cortex and of serotonin in corpus striatum. Moreover, aspartame treatment significantly alters the tyrosine hydroxylase activity and amino acids levels in the brain. Our data suggest that chronic use of aspartame may affect electrolyte homeostasis and monoamine neurotransmitter synthesis dose dependently, and this might have a possible effect on cognitive functions. © The Author(s) 2014.

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

PubMed

Lee, Choongyeop; Joly, Laurent; Siria, Alessandro; Biance, Anne-Laure; Fulcrand, Rémy; Bocquet, Lydéric

2012-08-08

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

Evaluation of Carbon Composite Overwrap Pressure Vessels Fabricated Using Ionic Liquid Epoxies Project

NASA Technical Reports Server (NTRS)

Grugel, Richard

2015-01-01

The intent of the work proposed here is to ascertain the viability of ionic liquid (IL) epoxy based carbon fiber composites for use as storage tanks at cryogenic temperatures. This IL epoxy has been specifically developed to address composite cryogenic tank challenges associated with achieving NASA's in-space propulsion and exploration goals. Our initial work showed that an unadulterated ionic liquid (IL) carbon-fiber composite exhibited improved properties over an optimized commercial product at cryogenic temperatures. Subsequent investigative work has significantly improved the IL epoxy and our first carbon-fiber Composite Overwrap Pressure Vessel (COPV) was successfully fabricated. Here additional COPVs, using a further improved IL epoxy, will be fabricated and pressure tested at cryogenic temperatures with the results rigorously analyzed. Investigation of the IL composite for lower pressure liner-less cryogenic tank applications will also be initiated. It is expected that the current Technology Readiness Level (TRL) will be raised from about TRL 3 to TRL 5 where unambiguous predictions for subsequent development/testing can be made.

Trace detection of oxygen--ionic liquids in gas sensor design.

PubMed

Baltes, N; Beyle, F; Freiner, S; Geier, F; Joos, M; Pinkwart, K; Rabenecker, P

2013-11-15

This paper presents a novel electrochemical membrane sensor on basis of ionic liquids for trace analysis of oxygen in gaseous atmospheres. The faradaic response currents for the reduction of oxygen which were obtained by multiple-potential-step-chronoamperometry could be used for real time detection of oxygen down to concentrations of 30 ppm. The theoretical limit of detection was 5 ppm. The simple, non-expensive sensors varied in electrolyte composition and demonstrated a high sensitivity, a rapid response time and an excellent reproducibility at room temperature. Some of them were continuously used for at least one week and first results promise good long term stability. Voltammetric, impedance and oxygen detection studies at temperatures up to 200 °C (in the presence and absence of humidity and CO2) revealed also the limitations of certain ionic liquids for some electrochemical high temperature applications. Application areas of the developed sensors are control and analysis processes of non oxidative and oxygen free atmospheres. Copyright © 2013 Elsevier B.V. All rights reserved.

Characterization of L-type calcium channel activity in atrioventricular nodal myocytes from rats with streptozotocin-induced Diabetes mellitus

PubMed Central

Yuill, Kathryn H; Al Kury, Lina T; Howarth, Frank Christopher

2015-01-01

Cardiovascular complications are common in patients with Diabetes mellitus (DM). In addition to changes in cardiac muscle inotropy, electrical abnormalities are also commonly observed in these patients. We have previously shown that spontaneous cellular electrical activity is altered in atrioventricular nodal (AVN) myocytes, isolated from the streptozotocin (STZ) rat model of type-1 DM. In this study, utilizing the same model, we have characterized the changes in L-type calcium channel activity in single AVN myocytes. Ionic currents were recorded from AVN myocytes isolated from the hearts of control rats and from those with STZ-induced diabetes. Patch-clamp recordings were used to assess the changes in cellular electrical activity in individual myocytes. Type-1 DM significantly altered the cellular characteristics of L-type calcium current. A reduction in peak ICaL density was observed, with no corresponding changes in the activation parameters of the current. L-type calcium channel current also exhibited faster time-dependent inactivation in AVN myocytes from diabetic rats. A negative shift in the voltage dependence of inactivation was also evident, and a slowing of restitution parameters. These findings demonstrate that experimentally induced type-1 DM significantly alters AVN L-type calcium channel cellular electrophysiology. These changes in ion channel activity may contribute to the abnormalities in cardiac electrical function that are associated with high mortality levels in patients with DM. PMID:26603460

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

PubMed

Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

2016-07-01

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid pretreatment of poplar wood at room temperature: swelling and incorporation of nanoparticles.

PubMed

Lucas, Marcel; Macdonald, Brian A; Wagner, Gregory L; Joyce, Stephen A; Rector, Kirk D

2010-08-01

Lignocellulosic biomass offers economic and environmental advantages over corn starch for biofuels production. However, its fractionation currently requires energy-intensive pretreatments, due to the lignin chemical resistance and complex cell wall structure. Recently, ionic liquids have been used to dissolve biomass at high temperatures. In this study, thin sections of poplar wood were swollen by ionic liquid (1-ethyl-3-methylimidazolium acetate) pretreatment at room temperature. The samples contract when rinsed with deionized water. The controlled expansion and contraction of the wood structure can be used to incorporate enzymes and catalysts deep into the wood structure for improved pretreatments and accelerated cellulose hydrolysis. As a proof of concept, silver and gold nanoparticles of diameters ranging from 20 to 100 nm were incorporated at depths up to 4 mum. Confocal surface-enhanced Raman images at different depths show that a significant number of nanoparticles were incorporated into the pretreated sample, and they remained on the samples after rinsing. Quantitative X-ray fluorescence microanalyses indicate that the majority of nanoparticle incorporation occurs after an ionic liquid pretreatment of less than 1 h. In addition to improved pretreatments, the incorporation of materials and chemicals into wood and paper products enables isotope tracing, development of new sensing, and imaging capabilities.

Enhancing the performance of green solid-state electric double-layer capacitor incorporated with fumed silica nanoparticles

NASA Astrophysics Data System (ADS)

Chong, Mee Yoke; Numan, Arshid; Liew, Chiam-Wen; Ng, H. M.; Ramesh, K.; Ramesh, S.

2018-06-01

Solid polymer electrolyte (SPE) based on fumed silica nanoparticles as nanofillers, hydroxylethyl cellulose (HEC) as host polymer, magnesium trifluoromethanesulfonate salt and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid is prepared by solution casting technique. The ionic conductivity, interactions of adsorbed ions on the host polymer, structural crystallinity and thermal stability are evaluated by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Ionic conductivity studies at room temperature reveals that the SPE with 2 wt. % of fumed silica nanoparticles gives the highest conductivity compared to its counterpart. The XRD and FTIR studies confirm the dissolution of salt, ionic liquid and successful incorporation of fumed silica nanoparticles with host polymer. In order to examine the performance of SPEs, electric double-layer capacitor (EDLC) are fabricated by using activated carbon electrodes. EDLC studies demonstrate that SPE incorporated with 2 wt. % fumed silica nanoparticles gives high specific capacitance (25.0 F/g) at a scan rate of 5 mV/s compared to SPE without fumed silica. Additionally, it is able to withstand 71.3% of capacitance from its initial capacitance value over 1600 cycles at a current density of 0.4 A/g.

Ionic Liquid-Modified Thermosets and Their Nanocomposites: Dispersion, Exfoliation, Degradation, and Cure

NASA Astrophysics Data System (ADS)

Throckmorton, James A.

This dissertation explores the application of a room temperature ionic liquid (RTIL) to problems in the chemistry, processing, and modification of thermosetting polymers. In particular, the solution properties and reaction chemistry of 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-DCN) are applied to problems of nanoparticle dispersion and processing, graphite exfoliation, cyanate ester (CE) cure, and the environmental degradation of CEs. Nanoparticle Dispersion: Nanocomposite processing can be simplified by using the same compound as both a nanoparticle solvent and an initiator for polymerization. This dual-function molecule can be designed both for solvent potential and reaction chemistry. EMIM-DCN, previously shown by our lab to act as an epoxy initiator, is used in the synthesis of silica and acid expanded graphite composites. These composites are then characterized for particle dispersion and physical properties. Individual particle dispersion of silica nanocomposites is shown, and silica nanocomposites at low loading show individual particle dispersion and improved modulus and fracture toughness. GNP nanocomposites show a 70% increase in modulus along with a 10-order of magnitude increase in electrical conductivity at 6.5 vol%, and an electrical percolation threshold of 1.7 vol%. Direct Graphite Exfoliation By Laminar Shear: This work presents a laminar-shear alternative to chemical processing and chaotic flow-fields for the direct exfoliation of graphite and the single-pot preparation of nanocomposites. Additionally, we develop the theory of laminar flow through a 3-roll mill, and apply that theory to the latest developments in the theory of graphite interlayer shear. The resulting nanocomposite shows low electrical percolation (0.5 vol%) and low thickness (1-3 layer) graphite/graphene flakes. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix properties and provide insight into the theory of the chemical and physical exfoliation of graphite crystals and the resulting polymer matrix dispersion. Cyanate Ester Cure: Dicyanamide-containing ionic liquids decrease the cure temperature of bi- and tri-functional CEs. During the cure reaction, the dicyanamide anion completely reacts and is incorporated into the triazine network. The cure effect was found in many dicyanamide-containing ionic liquids with diverse cations. This invention creates a novel, ionic thermoset polymer. The dicyanamide initiator provides an alternative to metal and hydroxyl catalysts (which have been shown to accelerate degradation and possess human and environmental toxicity). Additionally, the ionic character of the new polymer, rare among thermosets, lends itself to future research and novel applications. RTIL initiation also paves the way to new CE technologies, including RTIL-CE nanocomposites, prepared by graphite exfoliation and nanocomposite dispersion techniques developed herin.

THEORETICAL AND EXPERIMENTAL MODELING OF MULTI-SPECIES TRANSPORT IN SOILS UNDER ELECTRIC FIELDS

EPA Science Inventory

Electrokinetics employs the use of electrodes implanted in soils-contaminated media. Electrodes are supplied with direct current (dc) facilitating ionic transport and subsequent removal. This project investigates the feasibility and efficiency of electrokinetic transport of lea...

DIFMOD2: A NEXT GENERATION DIFFUSE LAYER MODEL

EPA Science Inventory

Jenne (1998) suggested that the majority of uncertainty in our current ability to model the environmental partitioning behavior of ionic species on natural surfaces resulted from uncertainties in our understanding of surface acidity behavior. Traditional 2-pK Grahame-Gouy-Chapma...

The Electrochemical Properties of Sr(Ti,Fe)O 3-δ for Anodes in Solid Oxide Fuel Cells

DOE PAGES

Nenning, Andreas; Volgger, Lukas; Miller, Elizabeth; ...

2017-02-18

Reduction-stable mixed ionic and electronic conductors such as Sr(Ti,Fe)O 3-δ (STF) are promising materials for application in anodes of solid oxide fuel cells. The defect chemistry of STF and its properties as solid oxide fuel cell (SOFC) cathode have been studied thoroughly, while mechanistic investigations of its electrochemical properties as SOFC anode material are still scarce. In this study, thin film model electrodes of STF with 30% and 70% Fe content were investigated in H 2+H 2O atmosphere by electrochemical impedance spectroscopy. Lithographically patterned thin film Pt current collectors were applied on top or beneath the STF thin films tomore » compensate for the low electronic conductivity under reducing conditions. Oxygen exchange resistances, electronic and ionic conductivities and chemical capacitances were quantified and discussed in a defect chemical model. Increasing Fe content increases the electro-catalytic activity of the STF surface as well as the electronic and ionic conductivity. Current collectors on top also increase the electrochemical activity due to a highly active Pt-atmosphere-STF triple phase boundary. Furthermore, the electrochemical activity depends decisively on the H 2:H 2O mixing ratio and the polarization. Lastly, Fe 0 nanoparticles may evolve on the surface in hydrogen rich atmospheres and increase the hydrogen adsorption rate.« less

Macroscopic strain controlled ion current in an elastomeric microchannel

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

Kuo, Chin-Chang; Nguyen, Du; Buchsbaum, Steven

We report on the fabrication of an ultra-high aspect ratio ionically conductive single microchannel with tunable diameter from ≈ 20 μm to fully closed. The 4 mm-long channel is fabricated in a Polydimethylsiloxane (PDMS) mold and its cross-sectional area is controlled by applying macroscopic compressive strain to the mold in a direction perpendicular to the channel length. We investigated the ionic conduction properties of the channel. For a wide range of compressive strain up to ≈ 0.27, the strain dependence of the resistance is monotonic and fully reversible. For strain > 0.27, ionic conduction suddenly shuts off and the system becomes hystereticmore » (whereby a finite strain reduction is required to reopen the channel). Upon unloading, the original behavior is retrieved. This reversible behavior is observed over 200 compression cycles. The cross-sectional area of the channel can be inferred from the ion current measurement, as confirmed by a Nano-Computed Tomography investigation. We show that the cross-sectional area decreases monotonically with the applied compressive strain in the reversible range, in qualitative agreement with linear elasticity theory. We find that the shut-off strain is affected by the spatial extent of the applied strain, which provides additional tunability. Our tunable channel is well-suited for multiple applications in micro/nano-fluidic devices.« less

Nucleobase recognition at alkaline pH and apparent pKa of single DNA bases immobilised within a biological nanopore.

PubMed

Franceschini, Lorenzo; Mikhailova, Ellina; Bayley, Hagan; Maglia, Giovanni

2012-02-01

The four DNA bases are recognized in immobilized DNA strands at high alkaline pH by nanopore current recordings. Ionic currents through the biological nanopores are also employed to measure the apparent pK(a) values of single nucleobases within the immobilised DNA strands. This journal is © The Royal Society of Chemistry 2012

Individual and community responses in stream mesocosms with different ionic compositions of conductivity and compared to a field-based benchmark

EPA Science Inventory

Several anthropogenic activities cause excess total dissolved solids (TDS) content and its correlate, specific conductivity, in surface waters due to increases in the major geochemical ions (e.g., Na, Ca, Cl, SO4). However, the relative concentrations of major ions varies with t...

On the origin of high ionic conductivity in Na-doped SrSiO 3

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

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

An Ionic Liquid Reaction and Separation Process for Production of Hydroxymethylfurfural from Sugars

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

Liu, Wei; Zheng, Feng; Li, Joanne

2014-01-01

There has been world-wide interest to making plastics out of renewable biomass feedstock for recent years. Hydroxymethylfurfural (HMF) is viewed as an attractive alternate to terephthalic acid (TPA) for production of polyesters (PET) and polyamides. Conversion of sugars into HMF has been studied in numerous publications. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. Different adsorbent materials are evaluated and silicalite material is demonstrated effective for isolation of 99% pure HMF from actual ionic liquid reaction mixtures and for recovery of the un-converted sugars and reaction intermediatemore » along with the ionic liquid. Membrane-coated silicalite particles are prepared and studied for a practical adsorption process operated at low pressure drops but with separation performances comparable or better than the powder material. Complete conversion of fresh fructose feed into HMF in the recycled ionic liquid is shown under suitable reaction conditions. Stability of HMF product is characterized. A simplified process flow diagram is proposed based on these research results, and the key equipment such as reactor and adsorbent bed is sized for a plant of 200,000 ton/year of fructose processing capacity. The proposed HMF production process is much simpler than the current paraxylene (PX) manufacturing process from petroleum oil, which suggests substantial reduction to the capital cost and energy consumption be possible. At the equivalent value to PX on the molar basis, there can be a large gross margin for HMF production from fructose and/or sugars.« less

Measuring blocking force to interpret ionic mechanisms within bucky-gel actuators

NASA Astrophysics Data System (ADS)

Kruusamäe, Karl; Sugino, Takushi; Asaka, Kinji

2015-04-01

Bucky-gel laminates are tri-layer structures where polymeric electrolyte film is sandwiched between two compliant electrode layers of carbon nanotubes and ionic liquid. The resulting ionic and capacitive structures, being regarded as a type of electromechanically active polymers (EAP), have the perspective of becoming soft bending actuators in the fields such as biomimetic robotics or lab-on-chip technology. A typical electromechanical step response of a bucky-gel actuator in a cantilever configuration exhibits a fast bending displacement followed by some reverse motion referred to as the back-relaxation. It has been proposed that the bending but also the back-relaxation of bucky-gel laminates occur due to the relocation of cations and anions within the tri-layer structure. A great number of modeling about ionic EAP materials aims to predict the amplitude of free bending or the blocking force of the actuator. However, as the bucky-gel laminates are viscoelastic, the translation from generated force to bending amplitude is not always straightforward - it can take the form of an integro-differential equation with speed (i.e. the amplitude and type of the input signal) and temperature (i.e. the electronic conductivity of the material and driving current) as just some of the parameters. In this study we propose to use a so-called two carrier-model to analyze the electromechanical response of a bucky-gel actuator. After modifying the electrical equivalent circuit, the time domain response of blocking force is measured to elaborate the ionic mechanisms during the work-cycle of bucky-gel actuator.

On the origin of high ionic conductivity in Na-doped SrSiO 3

DOE PAGES

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen; ...

2016-02-17

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Silver Nanoparticles and Ionic Silver Have Opposite Effects on Spontaneous Activity and Pharmacological Responses in Neuronal Networks In Vitro

EPA Science Inventory

CONTROL ID: 1850472 CONTACT (NAME ONLY): Timothy Shafer Abstract Details PRESENTATION TYPE: Platform or Poster CURRENT CATEGORY: Nanotoxicology, In Vitro | Neurotoxicity, General | Neurotoxicity, Metals KEYWORDS: Nanoparticle, Neurotoxicity, microelectrode array. DATE/TIME LAST...

Characteristics of switching plasma in an inverse-pinch switch

NASA Technical Reports Server (NTRS)

Lee, Ja H.; Choi, Sang H.; Venable, Demetrius D.; Han, Kwang S.; Nam, Sang H.

1993-01-01

Characteristics of the plasma that switches on tens of giga volt-ampere in an inverse-pinch plasma switch (INPIStron) have been made. Through optical and spectroscopic diagnostics of the current carrying plasma, the current density, the motion of current paths, dominant ionic species have been determined in order to access their effects on circuit parameters and material erosion. Also the optimum operational condition of the plasma-puff triggering method required for azimuthally uniform conduction in the INPIStron has been determined.

Polar localization of plasma membrane Ca2+/Mg2+ ATPase correlates with the pattern of steady ionic currents in eggs ofLymnaea stagnalis andBithynia tentaculata (Mollusca).

PubMed

Zivkovic, Danica; Créton, Robbert; Zwaan, Gideon; de Bruijn, Willem C; Dohmen, M René

1990-11-01

During extrusion of the first polar body in eggs ofLymnaea stagnalis andBithynia tentaculata a localized Ca 2+ /Mg 2+ ATPase activity was detected, using Ando's enzyme-cytochemical method for electron microscopy [Ando et al. (1981) Acta Histochem Cytochem 14:705-726]. The enzyme activity was distributed in a polar fashion, along the cytoplasmic face of the plasma membrane. In the eggs ofLymnaea it was found only in the vegetal hemisphere, whereas inBithynia eggs it was localized both in the vegetal hemisphere and at the animal pole. This pattern of enzyme activity corresponds to the polar pattern of transcellular ionic currents measured with the vibrating probe, which we showed to be partially carried or regulated by calcium [Zivkovic and Dohmen (1989) Biol Bull (Woods Hole) 176 (Suppl):103-109]. The characteristics of the ATPase were studied using a variety of approaches such as ion and substrate depletions and substitutions, addition of specific inhibitors of ATPase activity, treatment with EDTA/EGTA and electron energy-loss spectrometry. The results indicate that, inLymnaea, there are at least two enzymatic entities. The first one is a Ca 2+ /Mg 2+ ATPase localized along the membrane and in the cortex of the vegetal hemisphere. The second one is a Ca 2+ -stimulated ATPase (calcium pump of the plasma membrane) localized in a small region of the membrane at the vegetal pole. We speculate that in the eggs ofLymnaea andBithynia a functional relationship exists between the plasma-membrane-associated ATPase activity and the transcellular ionic currents measured in the same region.

Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.; Balke, N.; Kalinin, S. V.

2010-09-01

Electrochemical insertion-deintercalation reactions are typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrates the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10-nm level using electromechanical detection.

Pd-Catalyzed Heterocycle Synthesis in Ionic Liquids

NASA Astrophysics Data System (ADS)

Li, Jianxiao; Jiang, Huanfeng

Heterocyclic and fused heterocyclic compounds are ubiquitously found in natural products and biologically interesting molecules, and many currently marketed drugs hold heterocycles as their core structure. In this chapter, recent advances on Pd-catalyzed synthesis of heterocycles in ionic liquids (ILs) are reviewed. In palladium catalysis, ILs with different cations and anions are investigated as an alternative recyclable and environmentally benign reaction medium, and a variety of heterocyclic compounds including cyclic ketals, quinolones, quinolinones, isoindolinones, and lactones are conveniently constructed. Compared to the traditional methods, these new approaches have many advantages, such as environmentally friendly synthetic procedure, easy product and catalyst separation, recyclable medium, which make them have the potential applications in industry.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM

2006-10-10

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Corrosion of stainless steel battery components by bis(fluorosulfonyl)imide based ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Evans, Tyler; Olson, Jarred; Bhat, Vinay; Lee, Se-Hee

2014-12-01

While the anodic behavior of aluminum foil current collectors in imide-based room temperature ionic liquids (RTILs) is relatively well understood, interactions between such RTILs and other passive battery components have not been studied extensively. This study presents the solvent and potential dependent oxidation of SS316 coin-cell components in the N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (PYR13FSI) RTIL. While this phenomenon prohibits high-voltage cycling of Li(Ni1/3Mn1/3Co1/3)O2 cathodes in SS316 coin-type cells, Al-clad cell components or alternative cell configurations can be utilized to avoid SS316 oxidation-induced cell failure.

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

NASA Astrophysics Data System (ADS)

Widanarto, W.; Ramdhan, A. M.; Ghoshal, S. K.; Effendi, M.; Cahyanto, W. T.; Warsito

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10-7 S cm-1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

Cardiac tissue geometry as a determinant of unidirectional conduction block: assessment of microscopic excitation spread by optical mapping in patterned cell cultures and in a computer model.

PubMed

Fast, V G; Kléber, A G

1995-05-01

Unidirectional conduction block (UCB) and reentry may occur as a consequence of an abrupt tissue expansion and a related change in the electrical load. The aim of this study was to evaluate critical dimensions of the tissue necessary for establishing UCB in heart cell culture. Neonatal rat heart cell cultures with cell strands of variable width emerging into a large cell area were grown using a technique of patterned cell growth. Action potential upstrokes were measured using a voltage sensitive dye (RH-237) and a linear array of 10 photodiodes with a 15 microns resolution. A mathematical model was used to relate action potential wave shapes to underlying ionic currents. UCB (block of a single impulse in anterograde direction - from a strand to a large area - and conduction in the retrograde direction) occurred in narrow cell strands with a width of 15(SD 4) microns (1-2 cells in width, n = 7) and there was no conduction block in strands with a width of 31(8) microns (n = 9, P < 0.001) or larger. The analysis of action potential waveshapes indicated that conduction block was either due to geometrical expansion alone (n = 5) or to additional local depression of conduction (n = 2). In wide strands, action potential upstrokes during anterograde conduction were characterised by multiple rising phases. Mathematical modelling showed that two rising phases were caused by electronic current flow, whereas local ionic current did not coincide with the rising portions of the upstrokes. (1) High resolution optical mapping shows multiphasic action potential upstrokes at the region of abrupt expansion. At the site of the maximum decrement in conduction, these peaks were largely determined by the electrotonus and not by the local ionic current. (2) Unidirectional conduction block occurred in strands with a width of 15(4) microns (1-2 cells).

Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions.

PubMed

Rinne, Klaus F; Gekle, Stephan; Netz, Roland R

2014-12-07

Using extensive equilibrium molecular dynamics simulations we determine the dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-specific and concentration-dependent shifts of the static dielectric constants and the dielectric relaxation times match experimental results very well, which serves as a validation of the classical and non-polarizable ionic force fields used. The purely ionic contribution to the dielectric response is negligible, but determines the conductivity of the salt solutions. The ion-water cross correlation contribution is negative and reduces the total dielectric response by about 5%-10% for 1 M solutions. The dominating water dielectric response is decomposed into different water solvation shells and ion-pair configurations, by this the spectral blue shift and the dielectric decrement of salt solutions with increasing salt concentration is demonstrated to be primarily caused by first-solvation shell water. With rising salt concentration the simulated spectra show more pronounced deviations from a single-Debye form and can be well described by a Cole-Cole fit, in quantitative agreement with experiments. Our spectral decomposition into ionic and different water solvation shell contributions does not render the individual contributions more Debye-like, this suggests the non-Debye-like character of the dielectric spectra of salt solutions not to be due to the superposition of different elementary relaxation processes with different relaxation times. Rather, the non-Debye-like character is likely to be an inherent spectral signature of solvation water around ions.

Monitoring the ionic content of exhaled breath condensate in various respiratory diseases by capillary electrophoresis with contactless conductivity detection.

PubMed

Greguš, Michal; Foret, František; Kindlová, Dagmar; Pokojová, Eva; Plutinský, Marek; Doubková, Martina; Merta, Zdeněk; Binková, Ilona; Skřičková, Jana; Kubáň, Petr

2015-05-06

The analysis of an ionic profile of exhaled breath condensate (EBC) by capillary electrophoresis with contactless conductivity detection and double opposite end injection, is demonstrated. A miniature sampler made from a 2 ml syringe and an aluminium cooling cylinder was used for the fast collection of EBC (under one minute). Analysis of the collected EBC was performed in a 60 mM 2-(N-morpholino)ethanesulfonic acid, 60 mM L-histidine background electrolyte with 30 µM cetyltrimethylammonium bromide and 2 mM 18-crown-6 at pH 6, and excellent repeatability of migration times (RSD  <1.3% (n = 7)) and peak areas (RSD  <  7% (n = 7)) of 14 ions (inorganic anions, cations and organic acids) was obtained. It is demonstrated that the analysis of EBC samples obtained from patients with various respiratory diseases (chronic obstructive pulmonary disease, asthma, pulmonary fibrosis, sarcoidosis, cystic fibrosis) is possible in less than five minutes and the ionic profile can be compared with the group of healthy individuals. The analysis of the ionic profile of EBC samples provides a set of data in which statistically significant differences among the groups of patients could be observed for several clinically relevant anions (nitrite, nitrate, acetate, lactate). The developed collection system and method provides a highly reproducible and fast way of collecting and analyzing EBC, with future applicability in point-of-care diagnostics.

Safe Direct Current Stimulation to Expand Capabilities of Neural Prostheses

PubMed Central

Fridman, Gene Y.; Della Santina, Charles C.

2014-01-01

While effective in treating some neurological disorders, neuroelectric prostheses are fundamentally limited because they must employ charge-balanced stimuli to avoid evolution of irreversible electrochemical reactions and their byproducts at the interface between metal electrodes and body fluids. Charge-balancing is typically achieved by using brief biphasic alternating current (AC) pulses, which typically excite nearby neural tissues but cannot efficiently inhibit them. In contrast, direct current (DC) applied via a metal electrode in contact with body fluids can excite, inhibit and modulate sensitivity of neurons; however, DC stimulation is biologically unsafe because it violates “safe charge injection” limits that have long been considered unavoidable constraints. In this report, we describe the design and fabrication of a safe DC stimulator (SDCS) that overcomes this constraint. The SCDS drives DC ionic current into target tissue via salt-bridge micropipette electrodes by switching valves in phase with AC square waves applied to metal electrodes contained within the device. This approach achieves DC ionic flow through tissue while still adhering to charge-balancing constraints at each electrode-saline interface. We show the SDCS’s ability to both inhibit and excite neural activity to achieve improved dynamic range during prosthetic stimulation of the vestibular part of the inner ear in chinchillas. PMID:23476007

Heat stress responses modulate calcium regulations and electrophysiological characteristics in atrial myocytes.

PubMed

Chen, Yao-Chang; Kao, Yu-Hsun; Huang, Chun-Feng; Cheng, Chen-Chuan; Chen, Yi-Jen; Chen, Shih-Ann

2010-04-01

Heat stress-induced responses change the ionic currents and calcium homeostasis. However, the molecular insights into the heat stress responses on calcium homeostasis remain unclear. The purposes of this study were to examine the mechanisms of heat stress responses on calcium handling and electrophysiological characteristics in atrial myocytes. We used indo-1 fluorimetric ratio technique and whole-cell patch clamp to investigate the intracellular calcium, action potentials, and ionic currents in isolated rabbit single atrial cardiomyocytes with or without (control) exposure to heat stress (43 degrees C, 15 min) 5+/-1 h before experiments. The expressions of sarcoplasmic reticulum ATPase (SERCA2a), and Na(+)-Ca(2+) exchanger (NCX) in the control and heat stress-treated atrial myocytes were evaluated by Western blot and real-time PCR. As compared with control myocytes, the heat stress-treated myocytes had larger sarcoplasmic reticulum calcium content and larger intracellular calcium transient with a shorter decay portion. Heat stress-treated myocytes also had larger L-type calcium currents, transient outward potassium currents, but smaller NCX currents. Heat stress responses increased the protein expressions, SERCA2a, NCX, and heat shock protein. However, heat stress responses did not change the RNA expression of SERCA2a and NCX. In conclusion, heat stress responses change calcium handling through protein but not RNA regulation. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Mechanism of wear and tribofilm formation with ionic liquids and ashless antiwear additives

NASA Astrophysics Data System (ADS)

Sharma, Vibhu

Increasingly stringent government regulation on emissions (EPA Emissions Standard Reference Guide and latest CAFE standards requiring an average fuel economy of 54.5 mpg (combined cars and trucks) by 2025) impose significant challenges to the automotive and lubricant industries calling for the development and implementation of lower viscosity ILSAC GF-5&6 and API-CJ4&5 oils which further limit the amount of SAPS and deposits in engines. Development of additives that result in lower ash content, volatility and anti-wear property plays a crucial role in being able to reach these standards. The current industrial additive technology i.e. zinc dialkyldithiophosphate (ZDDP) forms harmful deposits on catalytic convertor due to the volatility of Zn, S and P which, impairs its functionality and consequently results in higher emission from vehicles. In this research work, ionic liquids (IL's) that are non-volatile have been studied as new generation environment friendly antiwear additives along with other ashless anti-wear additives including boron based additives to overcome the current challenges of improving the fuel efficiency and reducing the amount of hazardous emissions. The goal of this thesis work is to study the tribological performance of selected IL's and develop a comprehensive understating of IL's chemistry and its consequences to their friction and wear outcomes. As first approach, various P, S and F based ionic liquids are studied for their tribological properties by analyzing the friction and wear results generated using standard tribological experiments. Following this, advanced surface characterization techniques such as X-ray absorption near edge structure (XANES) spectroscopy, SEM, Nano-indentation, SPM techniques are used to investigate the chemical-mechanical properties of the antiwear films. Results indicate that the tribological properties of ionic liquids depend on their solubility in base oil (BO) as well as their chemical interaction with the rubbing surfaces. To address the solubility issue of IL's in BO, ILs with longer alkyl chain structure were carefully selected which helped enhance the van der waals interaction between strongly polar ILs and non-polar base oil. The interaction of IL's with the metal surfaces was examined by analyzing the chemical-mechanical properties of the antiwear films formed. Results indicate that ionic liquids do react with the steel surfaces and form a protective antiwear film composed of iron polyphosphates i.e. short to medium chain length which results in improved wear protection. In addition, soluble boron additive (SB) chemistries were blended with ionic liquids to study the synergism between these two ashless antiwear chemistries. Addition of soluble boron additive (SB) to phosphorous based IL (P_DEHP) reduces the incubation time for antiwear film formation by forming boron oxide/boron phosphate film as early as the rubbing starts and subsequently a more durable iron phosphate film is formed providing long lasting wear protection. The synergistic interaction of boron chemistry with phosphorous based ionic liquids provides superior antiwear properties while eliminating volatile elements such as Zn and S from the additive technology.

Fractional Poisson-Nernst-Planck Model for Ion Channels I: Basic Formulations and Algorithms.

PubMed

Chen, Duan

2017-11-01

In this work, we propose a fractional Poisson-Nernst-Planck model to describe ion permeation in gated ion channels. Due to the intrinsic conformational changes, crowdedness in narrow channel pores, binding and trapping introduced by functioning units of channel proteins, ionic transport in the channel exhibits a power-law-like anomalous diffusion dynamics. We start from continuous-time random walk model for a single ion and use a long-tailed density distribution function for the particle jump waiting time, to derive the fractional Fokker-Planck equation. Then, it is generalized to the macroscopic fractional Poisson-Nernst-Planck model for ionic concentrations. Necessary computational algorithms are designed to implement numerical simulations for the proposed model, and the dynamics of gating current is investigated. Numerical simulations show that the fractional PNP model provides a more qualitatively reasonable match to the profile of gating currents from experimental observations. Meanwhile, the proposed model motivates new challenges in terms of mathematical modeling and computations.

Improving Lithium Therapeutics by Crystal Engineering of Novel Ionic Cocrystals

PubMed Central

2013-01-01

Current United States Food and Drug Administration (FDA)-approved lithium salts are plagued with a narrow therapeutic window. Recent attempts to find alternative drugs have identified new chemical entities, but lithium’s polypharmacological mechanisms for treating neuropsychiatric disorders are highly debated and are not yet matched. Thus, re-engineering current lithium solid forms in order to optimize performance represents a low cost and low risk approach to the desired therapeutic outcome. In this contribution, we employed a crystal engineering strategy to synthesize the first ionic cocrystals (ICCs) of lithium salts with organic anions. We are unaware of any previous studies that have assessed the biological efficacy of any ICCs, and encouragingly we found that the new speciation did not negatively affect established bioactivities of lithium. We also observed that lithium ICCs exhibit modulated pharmacokinetics compared to lithium carbonate. Indeed, the studies detailed herein represent an important advancement in a crystal engineering approach to a new generation of lithium therapeutics. PMID:24191685

ORGANIC-HIGH IONIC STRENGTH AQUEOUS SOLVENT SYSTEMS FOR SPIRAL COUNTER-CURRENT CHROMATOGRAPHY: GRAPHIC OPTIMIZATION OF PARTITION COEFFICIENT

PubMed Central

Zeng, Yun; Liu, Gang; Ma, Ying; Chen, Xiaoyuan; Ito, Yoichiro

2012-01-01

A new series of organic-high ionic strength aqueous two-phase solvents systems was designed for separation of highly polar compounds by spiral high-speed counter-current chromatography. A total of 21 solvent systems composed of 1-butanol-ethanol-saturated ammonium sulfate-water at various volume ratios are arranged according to an increasing order of polarity. Selection of the two-phase solvent system for a single compound or a multiple sample mixture can be achieved by two steps of partition coefficient measurements using a graphic method. The capability of the method is demonstrated by optimization of partition coefficient for seven highly polar samples including tartrazine (K=0.77), tryptophan (K=1.00), methyl green (K= 0.93), tyrosine (0.81), metanephrine (K=0.89), tyramine (K=0.98), and normetanephrine (K=0.96). Three sulfonic acid components in D&C Green No. 8 were successfully separated by HSCCC using the graphic selection of the two-phase solvent system. PMID:23467197

Improving lithium therapeutics by crystal engineering of novel ionic cocrystals.

PubMed

Smith, Adam J; Kim, Seol-Hee; Duggirala, Naga K; Jin, Jingji; Wojtas, Lukasz; Ehrhart, Jared; Giunta, Brian; Tan, Jun; Zaworotko, Michael J; Shytle, R Douglas

2013-12-02

Current United States Food and Drug Administration (FDA)-approved lithium salts are plagued with a narrow therapeutic window. Recent attempts to find alternative drugs have identified new chemical entities, but lithium's polypharmacological mechanisms for treating neuropsychiatric disorders are highly debated and are not yet matched. Thus, re-engineering current lithium solid forms in order to optimize performance represents a low cost and low risk approach to the desired therapeutic outcome. In this contribution, we employed a crystal engineering strategy to synthesize the first ionic cocrystals (ICCs) of lithium salts with organic anions. We are unaware of any previous studies that have assessed the biological efficacy of any ICCs, and encouragingly we found that the new speciation did not negatively affect established bioactivities of lithium. We also observed that lithium ICCs exhibit modulated pharmacokinetics compared to lithium carbonate. Indeed, the studies detailed herein represent an important advancement in a crystal engineering approach to a new generation of lithium therapeutics.

Water-Borne Endovascular Embolics Inspired by the Undersea Adhesive of Marine Sandcastle Worms.

PubMed

Jones, Joshua P; Sima, Monika; O'Hara, Ryan G; Stewart, Russell J

2016-04-06

Transcatheter embolization is used to treat vascular malformations and defects, to control bleeding, and to selectively block blood supply to tissues. Liquid embolics are used for small vessel embolization that require distal penetration. Current liquid embolic agents have serious drawbacks, mostly centered around poor handling characteristics and toxicity. In this work, a water-borne in situ setting liquid embolic agent is described that is based on electrostatically condensed, oppositely charged polyelectrolytes-complex coacervates. At high ionic strengths, the embolic coacervates are injectable fluids that can be delivered through long narrow microcatheters. At physiological ionic strength, the embolic coacervates transition into a nonflowing solid morphology. Transcatheter embolization of rabbit renal arteries demonstrated capillary level penetration, homogeneous occlusion, and 100% devascularization of the kidney, without the embolic crossing into venous circulation. The benign water-borne composition and setting mechanism avoids many of the problems of current liquid embolics, and provides precise temporal and spatial control during endovascular embolization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bradykinin induced a positive chronotropic effect via stimulation of T- and L-type calcium currents in heart cells.

PubMed

El-Bizri, Nesrine; Bkaily, Ghassan; Wang, Shimin; Jacques, Danielle; Regoli, Domenico; D'Orléans-Juste, Pedro; Sukarieh, Rami

2003-03-01

Using Fluo-3 calcium dye confocal microscopy and spontaneously contracting embryonic chick heart cells, bradykinin (10(-10) M) was found to induce positive chronotropic effects by increasing the frequency of the transient increase of cytosolic and nuclear free Ca2+. Pretreatment of the cells with either B1 or B2 receptor antagonists (R126 and R817, respectively) completely prevented bradykinin (BK) induced positive chronotropic effects on spontaneously contracting single heart cells. Using the whole-cell voltage clamp technique and ionic substitution to separate the different ionic current species, our results showed that BK (10(-6) M) had no effect on fast Na+ inward current and delayed outward potassium current. However, both L- and T-type Ca2+ currents were found to be increased by BK in a dose-dependent manner (10(-10)-10(-7) M). The effects of BK on T- and L-type Ca2+ currents were partially blocked by the B1 receptor antagonist [Leu8]des-Arg9-BK (R592) (10(-7) M) and completely reversed by the B2 receptor antagonist D-Arg[Hyp3,D-Phe7,Leu8]BK (R-588) (10(-7) M) or pretreatment with pertussis toxin (PTX). These results demonstrate that BK induced a positive chronotropic effect via stimulation of T- and L-type Ca2+ currents in heart cells mainly via stimulation of B2 receptor coupled to PTX-sensitive G-proteins. The increase of both types of Ca2+ current by BK in heart cells may explain the positive inotropic and chronotropic effects of this hormone.

Study of Parameters Dominating Electromechanical and Sensing Response in Ionic Electroactive Polymer (IEAP) Transducers

NASA Astrophysics Data System (ADS)

Almomani, Abdallah Mohammad

Ionic electroactive polymer (IEAP) transducers are a class of smart structures based on polymers that can be designed as soft actuators or sensors. IEAP actuators exhibit a high mechanical response to an external electrical stimulus. Conversely, they produce electrical signals when subjected to mechanical force. IEAP transducers are mainly composed of four different components: The ionomeric membrane (usually Nafion) is an ion permeable polymer that acts as the backbone of the transducer. Two conductive network composite (CNC) layer on both sides of the ionomeric membrane that enhance the surface conductivity and serve as an extra reservoir to the electrolytes. The electrolytes, (usually ionic liquids (IL)), which provides the mobile ions. And two outer electrodes on both sides of the transducer to either provide a distributed applied potential across the actuators (usually gold leaves) or to collect the generated signals from the sensors (usually copper electrodes). Any variation in any of these components or the operating conditions will directly affect the performance of the IEAP transduces. In this dissertation, we studied some of the parameters dominating the performance of the IEAP transducers by varying some of the transducers components or the transducers operating conditions in order to enhance their performance. The first study was conducted to understand the influence of ionic liquid concentration on the electromechanical performance of IEAP actuators. The IL weight percentage (wt%) was varied from 10% to 30% and both the electromechanical (induced strain) and the electrochemical (the current flow across the actuators) were studied. The results from this study showed an enhanced electrochemical performance (current flow is higher for higher IL wt%) and a maximum electromechanical strain of approximately 1.4% at 22 wt% IL content. A lower induced strain was noticed for IL wt% lower or higher than 22%. The second study was to investigate the effect of changing the morphology of the CNC on the sensing performance of IEAP stress sensors. In this study, small salt molecules were added to the CNC layers. Salt molecules directly affected the morphology of the CNC layers resulting in a thicker, more porous, and high conductive CNCs. As a result, the ionic conductivity increased through the CNC layers and sensing performance was enhanced significantly. In the third study, a non-linear angular deformation (limb-like motion) was achieved by varying the CNC layers of the IEAP actuators by adding some conjugated polymers (CP) patterns during the fabrication of the actuators. It was found that the segments with the CP layers will only expand and never contract during the actuation process. Depending on the direction of motion and the location of the CP layers, different actuation shapes such as square or triangular shapes were achieved rather than the typical circular bending. In the fourth study, the influence of temperature on the electromechanical properties of the IEAP actuators was examined. In this study, both electromechanical and electrochemical studies were conducted for actuators that were operated at temperatures ranging from 25 °C to 90 °C. The electromechanical results showed a lower cationic curvature with increasing temperature up to 70 °C. On the other hand, a maximum anionic curvature was achieved at 50 °C with a sudden decrease after 50 °C. Actuators started to lose functionality and showed unpredictable performance at temperatures higher than 70 °C. Electrochemically, an enhancement of the ionic conductivity was resulted from increasing temperature up to 80 °C. A sudden increase in current flow was recorded at 90 °C indicating a shorted circuit and actuator failure. Finally, in the fifth study, protons in Nafion membranes were exchanged with other counterions of different Van der Waals volumes. The ionic conductivity was measured for IEAP membranes with different counterions at different temperatures. The results showed higher ionic conductivities across membranes with larger Van der Waals volume counterions and higher temperatures. A different ionic conductivity behavior was also noticed for temperatures ranging from 30 °C to 55 °C than temperatures between 55 °C and 70 °C after fitting the data with the Arrhenius conductivity equation.

Large heat capacity change in a protein-monovalent cation interaction.

PubMed

Guinto, E R; Di Cera, E

1996-07-09

Current views about protein-ligand interactions state that electrostatic forces drive the binding of charged species and that burial of hydrophobic and polar surfaces controls the heat capacity change associated with the reaction. For the interaction of a protein with a monovalent cation the electrostatic components are expected to be significant due to the ionic nature of the ligand, whereas the heat capacity change is expected to be small due to the size of the surface area involved in the recognition event. The physiologically important interaction of Na+ with thrombin was studied over the temperature range from 5 to 45 degrees C and the ionic strength range from 50 to 800 mM. These measurements reveal an unanticipated result that bears quite generally on studies of molecular recognition and protein folding. Binding of Na+ to thrombin is characterized by a modest dependence on ionic strength but a large and negative heat capacity change of -1.1 +/- 0.1 kcal mol-1 K-1. The small electrostatic coupling can be explained in terms of a minimal perturbation of the ionic atmosphere of the protein upon Na+ binding. The large heat capacity change, however, is difficult to reconcile with current views on the origin of this effect from surface area changes or large folding transitions coupled to binding. It is proposed that this change is linked to burial of a large cluster of water molecules in the Na+ binding pocket upon Na+ binding. Due to their reduced mobility and highly ordered structure, water molecules sequestered in the interior of a protein must have a lower heat capacity compared to those on the surface of a protein or in the bulk solvent. Hence, a binding or folding event where water molecules are buried may result in significant heat capacity changes independent of changes in exposed hydrophobic surface or coupled conformational transitions.

Sr- and Nb-co-doped Li7La3Zr2O12 solid electrolyte with Al2O3 addition towards high ionic conductivity

NASA Astrophysics Data System (ADS)

Lin, Changwei; Tang, Yu; Song, Jun; Han, Lei; Yu, Jingbo; Lu, Anxian

2018-06-01

In the present study, series of garnet-type Li6.75+ x La3- x Sr x Zr1.75Nb0.25O12 solid electrolytes [LLSZN with various Sr contents ( x = 0.05-0.25)] have been prepared via conventional solid-state method. The effects of Sr contents on their phase structure and ionic conductivity have been systematically investigated on the combined measurements of X-ray diffraction and scanning electron microscopy and alter current impedance spectroscopy. Our results reveal that a phase transition from tetragonal to cubic structure occurs when both Sr and Nb elements is introduced, and such a cubic structure can be stable over the whole Sr contents variation, which is suggested to provide a beneficial impact on the performance of LLSZN. Accordingly, both relative density and total ionic conductivity exhibit a favorable tendency of increasing first and then decreasing with increased Sr contents, wherein a peak value at 93.46% and 5.09 × 10-4 S cm-1, respectively, can be well achieved. Particularly, the maximum ionic conductivity is almost twice that of the compared sample (2.93 × 10-4 S cm-1), and possess the minimum activation energy 0.30 eV. Such a modification method, featured with higher efficiency and lower cost, is expected to be helpful for the development of solid electrolyte.

Improved Ionic Diffusion through the Mesoporous Carbon Skin on Silicon Nanoparticles Embedded in Carbon for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Kim, Hyeonjin; Ahn, Hyo-Jin

2018-02-21

Because of their combined effects of outstanding mechanical stability, high electrical conductivity, and high theoretical capacity, silicon (Si) nanoparticles embedded in carbon are a promising candidate as electrode material for practical utilization in Li-ion batteries (LIBs) to replace the conventional graphite. However, because of the poor ionic diffusion of electrode materials, the low-grade ultrafast cycling performance at high current densities remains a considerable challenge. In the present study, seeking to improve the ionic diffusion, we propose a novel design of mesoporous carbon skin on the Si nanoparticles embedded in carbon by hydrothermal reaction, poly(methyl methacrylate) coating process, and carbonization. The resultant electrode offers a high specific discharge capacity with excellent cycling stability (1140 mA h g -1 at 100 mA g -1 after 100 cycles), superb high-rate performance (969 mA h g -1 at 2000 mA g -1 ), and outstanding ultrafast cycling stability (532 mA h g -1 at 2000 mA g -1 after 500 cycles). The battery performances are surpassing the previously reported results for carbon and Si composite-based electrodes on LIBs. Therefore, this novel approach provides multiple benefits in terms of the effective accommodation of large volume expansions of the Si nanoparticles, a shorter Li-ion diffusion pathway, and stable electrochemical conditions from a faster ionic diffusion during cycling.

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

NASA Astrophysics Data System (ADS)

Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho

2018-07-01

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

Perfluoro anion based binary and ternary ionic liquids as electrolytes for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Lin, Hsi-Hsin; Peng, Jia-De; Suryanarayanan, V.; Velayutham, D.; Ho, Kuo-Chuan

2016-04-01

In this work, eight new ionic liquids (ILs) based on triethylammonium (TEA) or n-methylpiperidinium (NMP) cations and perfluoro carboxylate (PFC) anions having different carbon chain lengths are synthesized and their physico-chemical properties such as density, decomposition temperature, viscosity and conductivity are determined. Photovoltaic characteristics of dye-sensitized solar cells (DSSCs) with binary ionic liquids electrolytes, containing the mixture of the synthesized ILs and 1-methyl-3-propyl imidazolium iodide (PMII) (v/v = 35/65), are evaluated. Among the different ILs, solar cells containing NMP based ILs show higher VOC than that of TEA, whereas, higher JSC is noted for the DSSCs incorporated with the latter when compared to the former. Further, the photo-current of the DSSCs decreases with the increase of the carbon chain length of perfluoro carboxylate anionic group of ILs. The cell performance of the DSSC containing ternary ionic liquids-based electrolytes compose of NMP-2C/TEA-2C/PMII (v/v/v = 28/7/65) exhibits a JSC of 12.99 mA cm-2, a VOC of 639.0 mV, a FF of 0.72, and a cell efficiency of 6.01%. The extraordinary durability of the DSSC containing the above combination of electrolytes stored in dark at 50 °C is proved to be unfailing up to 1200 h.

Determination of urine ionic composition with potentiometric multisensor system.

PubMed

Yaroshenko, Irina; Kirsanov, Dmitry; Kartsova, Lyudmila; Sidorova, Alla; Borisova, Irina; Legin, Andrey

2015-01-01

The ionic composition of urine is a good indicator of patient's general condition and allows for diagnostics of certain medical problems such as e.g., urolithiasis. Due to environmental factors and malnutrition the number of registered urinary tract cases continuously increases. Most of the methods currently used for urine analysis are expensive, quite laborious and require skilled personnel. The present work deals with feasibility study of potentiometric multisensor system of 18 ion-selective and cross-sensitive sensors as an analytical tool for determination of urine ionic composition. In total 136 samples from patients of Urolithiasis Laboratory and healthy people were analyzed by the multisensor system as well as by capillary electrophoresis as a reference method. Various chemometric approaches were implemented to relate the data from electrochemical measurements with the reference data. Logistic regression (LR) was applied for classification of samples into healthy and unhealthy producing reasonable misclassification rates. Projection on Latent Structures (PLS) regression was applied for quantitative analysis of ionic composition from potentiometric data. Mean relative errors of simultaneous prediction of sodium, potassium, ammonium, calcium, magnesium, chloride, sulfate, phosphate, urate and creatinine from multisensor system response were in the range 3-13% for independent test sets. This shows a good promise for development of a fast and inexpensive alternative method for urine analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites

DOE PAGES

Wang, Yonggang; Wang, Qingfei; Liu, Zhenpu; ...

2015-06-10

High-performance solid electrolytes are critical for realizing all-solid-state batteries with enhance safety and cycling efficiency. However, currently available candidates (sulfides and the NASICON-typ ceramics) still suffer from drawbacks such as inflammability, high-cost and unfavorable machinability Here we present the structural manipulation approaches to improve the sodium ionic conductivity in series of affordable Na-rich antiperovskites. Experimentally, the whole solid solutions of Na 3OX (X ¼ Cl Br, I) are synthesized via a facile and timesaving route from the cheapest raw materials (Na, NaOH an NaX). The materials are nonflammable, suitable for thermoplastic processing due to low melting temperature (<300° C) withoutmore » decomposing. Notably, owing to the flexibility of perovskite-type structure it's feasible to control the local structure features by means of size-mismatch substitution an unequivalent-doping for a favorable sodium ionic diffusion pathway. Enhancement of sodium ioni conductivity by 2 magnitudes is demonstrated by these chemical tuning methods. The optimized sodiu ionic conductivity in Na 2.9Sr 0.05OBr 0.6I 0.4 bulk samples reaches 1.9 10 - 3 S/cm at 200° C and even highe at elevated temperature. Here, we believe further chemical tuning efforts on Na-rich antiperovskites wil promote their performance greatly for practical all-solid state battery applications.« less

Charge Density Dependent Hole Mobility and Density of States Throughout the Entire Finite Potential Window of Conductivity in Ionic Liquid Gated Poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.; Frisbie, C. Daniel

2012-02-01

Ionic liquids, used in place of traditional gate dielectric materials, allow for the accumulation of very high 2D and 3D charge densities (>10^14 #/cm^2 and >10^21 #/cm^3 respectively) at low voltage (<5 V). Here we study the electrochemical gating of the benchmark semiconducting polymer poly(3-hexylthiophene) (P3HT) with the ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMI][FAP]). The electrochemical stability of [EMI][FAP] allowed the reproducible accumulation of 2 x 10^21 hole/cm^3, or one hole (and stabilizing anion dopant) per every two thiophene rings. A finite potential/charge density window of high electrical conductivity was observed with hole mobility reaching a maximum of 0.86 cm^2/V s at 0.12 holes per thiophene ring. Displacement current measurements, collected versus a calibrated reference electrode, allowed the mapping of the highly structured and extremely broad density of states of the P3HT/[EMI][FAP] doped composite. Variable temperature and charge density hole transport measurements revealed hole transport to be thermally activated and non-monotonic, displaying a activation energy minimum of ˜20 meV in the region of maximum conductivity and hole mobility. To show the generality of this result, the study was extended to an additional four ionic liquids and three semiconducting polymers.

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

Graphene Nanopores for Protein Sequencing.

PubMed

Wilson, James; Sloman, Leila; He, Zhiren; Aksimentiev, Aleksei

2016-07-19

An inexpensive, reliable method for protein sequencing is essential to unraveling the biological mechanisms governing cellular behavior and disease. Current protein sequencing methods suffer from limitations associated with the size of proteins that can be sequenced, the time, and the cost of the sequencing procedures. Here, we report the results of all-atom molecular dynamics simulations that investigated the feasibility of using graphene nanopores for protein sequencing. We focus our study on the biologically significant phenylalanine-glycine repeat peptides (FG-nups)-parts of the nuclear pore transport machinery. Surprisingly, we found FG-nups to behave similarly to single stranded DNA: the peptides adhere to graphene and exhibit step-wise translocation when subject to a transmembrane bias or a hydrostatic pressure gradient. Reducing the peptide's charge density or increasing the peptide's hydrophobicity was found to decrease the translocation speed. Yet, unidirectional and stepwise translocation driven by a transmembrane bias was observed even when the ratio of charged to hydrophobic amino acids was as low as 1:8. The nanopore transport of the peptides was found to produce stepwise modulations of the nanopore ionic current correlated with the type of amino acids present in the nanopore, suggesting that protein sequencing by measuring ionic current blockades may be possible.

Nanopore analysis of polymers in solution.

NASA Astrophysics Data System (ADS)

Deamer, David

2002-03-01

Nanopores represent a novel approach for investigating macromolecules in solution. Polymers that have been analyzed by this technique include polyethylene glycol (PEG), certain proteins and nucleic acids. The a-hemolysin pore inserted into lipid bilayers provides continuous non-gated ion current through a pore diameter of approximately 1.5 - 2 nm. Nucleic acid molecules can be driven through the pore by imposing a voltage across the supporting membrane. Single stranded, but not double stranded nucleic acids pass through in strict linear sequence from one end of the molecule to the other. While in the pore, the molecule reduces ionic current, and properties of the ionic current blockade such as duration, mean amplitude and modulations of amplitude provide information about structure and composition of the nucleic acid. For a given molecular species, the duration of the blockade is a function of chain length, and the rate of blockades is linearly related to concentration. More recent studies have shown that the a-hemolysin nanopore can discriminate between synthetic DNA molecules differing by a single base pair or even a single nucleotide. These results indicate that a nanopore may have the resolution required for nucleic acid sequencing applications.

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength - Simple Conceptual Diagram

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength - Detailed Conceptual Diagram

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

Monoenergetic source of kilodalton ions from Taylor cones of ionic liquids

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

Larriba, C.; Castro, S.; Fernandez de la Mora, J.

2007-04-15

The ionic liquid ion sources (ILISs) recently introduced by Lozano and Martinez Sanchez [J. Colloid Interface Sci. 282, 415 (2005)], based on electrochemically etched tungsten tips as emitters for Taylor cones of ionic liquids (ILs), have been tested with ionic liquids [A{sup +}B{sup -}] of increasing molecular weight and viscosity. These ILs have electrical conductivities well below 1 S/m and were previously thought to be unsuitable to operate in the purely ionic regime because their Taylor cones produce mostly charged drops from conventional capillary tube sources. Strikingly, all the ILs tried on ILIS form charged beams composed exclusively of smallmore » ions and cluster ions A{sup +}(AB){sub n} or B{sup -}(AB){sub n}, with abundances generally peaking at n=1. Particularly interesting are the positive and negative ion beams produced from the room temperature molten salts 1-methyl-3-pentylimidazolium tris(pentafluoroethyl) trifluorophosphate (C{sub 5}MI-(C{sub 2}F{sub 5}){sub 3}PF{sub 3}) and 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) sulfonylimide (EMI-(C{sub 2}F{sub 5}SO{sub 3}){sub 2}N). We extend to these heavier species the previous conclusions from Lozano and Martinez Sanchez on the narrow energy distributions of the ion beams. In combination with suitable ILs, this source yields nanoamphere currents of positive and negative monoenergetic molecular ions with masses exceeding 2000 amu. Potential applications are in biological secondary ion mass spectrometry, chemically assisted high-resolution ion beam etching, and electrical propulsion. Advantages of the ILISs versus similar liquid metal ion sources include the possibility to form negative as well as positive ion beams and a much wider range of ion compositions and molecular masses.« less

Expression of naturally ionic liquid-tolerant thermophilic cellulases in Aspergillus niger

DOE PAGES

Amaike Campen, Saori; Lynn, Jed; Sibert, Stephanie J.; ...

2017-12-27

Efficient deconstruction of plant biomass is a major barrier to the development of viable lignocellulosic biofuels. Pretreatment with ionic liquids reduces lignocellulose recalcitrance to enzymatic hydrolysis, increasing yields of sugars for conversion into biofuels. However, commercial cellulases are not compatible with many ionic liquids, necessitating extensive water washing of pretreated biomass prior to hydrolysis. To circumvent this issue, previous research has demonstrated that several thermophilic bacterial cellulases can efficiently deconstruct lignocellulose in the presence of the ionic liquid, 1-ethyl-3-methylimadizolium acetate. As promising as these enzymes are, they would need to be produced at high titer in an industrial enzyme productionmore » host before they could be considered a viable alternative to current commercial cellulases. Aspergillus Niger has been used to produce high titers of secreted enzymes in industry and therefore, we assessed the potential of this organism to be used as an expression host for these ionic liquid-tolerant cellulases. We demonstrated that 29 of these cellulases were expressed at detectable levels in a wild-type strain of A. Niger, indicating a basic level of compatibility and potential to be produced at high levels in a host engineered to produce high titers of enzymes. We then profiled one of these enzymes in detail, the β-glucosidase A5IL97, and compared versions expressed in both A. Niger and Escherichia coli. Finally, this comparison revealed the enzymatic activity of A5IL97 purified from E. coli and A. Niger is equivalent, suggesting that A. Niger could be an excellent enzyme production host for enzymes originally characterized in E. coli, facilitating the transition from the laboratory to industry.« less

Expression of naturally ionic liquid-tolerant thermophilic cellulases in Aspergillus niger

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

Amaike Campen, Saori; Lynn, Jed; Sibert, Stephanie J.

Efficient deconstruction of plant biomass is a major barrier to the development of viable lignocellulosic biofuels. Pretreatment with ionic liquids reduces lignocellulose recalcitrance to enzymatic hydrolysis, increasing yields of sugars for conversion into biofuels. However, commercial cellulases are not compatible with many ionic liquids, necessitating extensive water washing of pretreated biomass prior to hydrolysis. To circumvent this issue, previous research has demonstrated that several thermophilic bacterial cellulases can efficiently deconstruct lignocellulose in the presence of the ionic liquid, 1-ethyl-3-methylimadizolium acetate. As promising as these enzymes are, they would need to be produced at high titer in an industrial enzyme productionmore » host before they could be considered a viable alternative to current commercial cellulases. Aspergillus Niger has been used to produce high titers of secreted enzymes in industry and therefore, we assessed the potential of this organism to be used as an expression host for these ionic liquid-tolerant cellulases. We demonstrated that 29 of these cellulases were expressed at detectable levels in a wild-type strain of A. Niger, indicating a basic level of compatibility and potential to be produced at high levels in a host engineered to produce high titers of enzymes. We then profiled one of these enzymes in detail, the β-glucosidase A5IL97, and compared versions expressed in both A. Niger and Escherichia coli. Finally, this comparison revealed the enzymatic activity of A5IL97 purified from E. coli and A. Niger is equivalent, suggesting that A. Niger could be an excellent enzyme production host for enzymes originally characterized in E. coli, facilitating the transition from the laboratory to industry.« less

Expression of Aspergillus niger CAZymes is determined by compositional changes in wheat straw generated by hydrothermal or ionic liquid pretreatments.

PubMed

Daly, Paul; van Munster, Jolanda M; Blythe, Martin J; Ibbett, Roger; Kokolski, Matt; Gaddipati, Sanyasi; Lindquist, Erika; Singan, Vasanth R; Barry, Kerrie W; Lipzen, Anna; Ngan, Chew Yee; Petzold, Christopher J; Chan, Leanne Jade G; Pullan, Steven T; Delmas, Stéphane; Waldron, Paul R; Grigoriev, Igor V; Tucker, Gregory A; Simmons, Blake A; Archer, David B

2017-01-01

The capacity of fungi, such as Aspergillus niger, to degrade lignocellulose is harnessed in biotechnology to generate biofuels and high-value compounds from renewable feedstocks. Most feedstocks are currently pretreated to increase enzymatic digestibility: improving our understanding of the transcriptomic responses of fungi to pretreated lignocellulosic substrates could help to improve the mix of activities and reduce the production costs of commercial lignocellulose saccharifying cocktails. We investigated the responses of A. niger to untreated, ionic liquid and hydrothermally pretreated wheat straw over a 5-day time course using RNA-seq and targeted proteomics. The ionic liquid pretreatment altered the cellulose crystallinity while retaining more of the hemicellulosic sugars than the hydrothermal pretreatment. Ionic liquid pretreatment of straw led to a dynamic induction and repression of genes, which was correlated with the higher levels of pentose sugars saccharified from the ionic liquid-pretreated straw. Hydrothermal pretreatment of straw led to reduced levels of transcripts of genes encoding carbohydrate-active enzymes as well as the derived proteins and enzyme activities. Both pretreatments abolished the expression of a large set of genes encoding pectinolytic enzymes. These reduced levels could be explained by the removal of parts of the lignocellulose by the hydrothermal pretreatment. The time course also facilitated identification of temporally limited gene induction patterns. The presented transcriptomic and biochemical datasets demonstrate that pretreatments caused modifications of the lignocellulose, to both specific structural features as well as the organisation of the overall lignocellulosic structure, that determined A. niger transcript levels. The experimental setup allowed reliable detection of substrate-specific gene expression patterns as well as hitherto non-expressed genes. Our data suggest beneficial effects of using untreated and IL-pretreated straw, but not HT-pretreated straw, as feedstock for CAZyme production.

Expression of naturally ionic liquid-tolerant thermophilic cellulases in Aspergillus niger

PubMed Central

Lynn, Jed; Sibert, Stephanie J.; Srikrishnan, Sneha; Phatale, Pallavi; Feldman, Taya; Guenther, Joel M.; Hiras, Jennifer; Tran, Yvette Thuy An; Singer, Steven W.; Adams, Paul D.; Sale, Kenneth L.; Simmons, Blake A.; Baker, Scott E.; Magnuson, Jon K.; Gladden, John M.

2017-01-01

Efficient deconstruction of plant biomass is a major barrier to the development of viable lignocellulosic biofuels. Pretreatment with ionic liquids reduces lignocellulose recalcitrance to enzymatic hydrolysis, increasing yields of sugars for conversion into biofuels. However, commercial cellulases are not compatible with many ionic liquids, necessitating extensive water washing of pretreated biomass prior to hydrolysis. To circumvent this issue, previous research has demonstrated that several thermophilic bacterial cellulases can efficiently deconstruct lignocellulose in the presence of the ionic liquid, 1-ethyl-3-methylimadizolium acetate. As promising as these enzymes are, they would need to be produced at high titer in an industrial enzyme production host before they could be considered a viable alternative to current commercial cellulases. Aspergillus niger has been used to produce high titers of secreted enzymes in industry and therefore, we assessed the potential of this organism to be used as an expression host for these ionic liquid-tolerant cellulases. We demonstrated that 29 of these cellulases were expressed at detectable levels in a wild-type strain of A. niger, indicating a basic level of compatibility and potential to be produced at high levels in a host engineered to produce high titers of enzymes. We then profiled one of these enzymes in detail, the β-glucosidase A5IL97, and compared versions expressed in both A. niger and Escherichia coli. This comparison revealed the enzymatic activity of A5IL97 purified from E. coli and A. niger is equivalent, suggesting that A. niger could be an excellent enzyme production host for enzymes originally characterized in E. coli, facilitating the transition from the laboratory to industry. PMID:29281693

Expression of naturally ionic liquid-tolerant thermophilic cellulases in Aspergillus niger.

PubMed

Amaike Campen, Saori; Lynn, Jed; Sibert, Stephanie J; Srikrishnan, Sneha; Phatale, Pallavi; Feldman, Taya; Guenther, Joel M; Hiras, Jennifer; Tran, Yvette Thuy An; Singer, Steven W; Adams, Paul D; Sale, Kenneth L; Simmons, Blake A; Baker, Scott E; Magnuson, Jon K; Gladden, John M

2017-01-01

Efficient deconstruction of plant biomass is a major barrier to the development of viable lignocellulosic biofuels. Pretreatment with ionic liquids reduces lignocellulose recalcitrance to enzymatic hydrolysis, increasing yields of sugars for conversion into biofuels. However, commercial cellulases are not compatible with many ionic liquids, necessitating extensive water washing of pretreated biomass prior to hydrolysis. To circumvent this issue, previous research has demonstrated that several thermophilic bacterial cellulases can efficiently deconstruct lignocellulose in the presence of the ionic liquid, 1-ethyl-3-methylimadizolium acetate. As promising as these enzymes are, they would need to be produced at high titer in an industrial enzyme production host before they could be considered a viable alternative to current commercial cellulases. Aspergillus niger has been used to produce high titers of secreted enzymes in industry and therefore, we assessed the potential of this organism to be used as an expression host for these ionic liquid-tolerant cellulases. We demonstrated that 29 of these cellulases were expressed at detectable levels in a wild-type strain of A. niger, indicating a basic level of compatibility and potential to be produced at high levels in a host engineered to produce high titers of enzymes. We then profiled one of these enzymes in detail, the β-glucosidase A5IL97, and compared versions expressed in both A. niger and Escherichia coli. This comparison revealed the enzymatic activity of A5IL97 purified from E. coli and A. niger is equivalent, suggesting that A. niger could be an excellent enzyme production host for enzymes originally characterized in E. coli, facilitating the transition from the laboratory to industry.

Preparation of giant myelin vesicles and proteoliposomes to register ionic channels.

PubMed

Regueiro, P; Monreal, J; Díaz, R S; Sierra, F

1996-11-01

Myelin vesicles, reconstituted liposomes with proteolipid protein (PLP), the main protein component of myelin, and electrophysiological patch-clamp are potentially powerful tools to study the role of myelin in functional ionic channels. However, technical difficulties in the vesiculation of myelin and the small size of the vesicles obtained do not permit the application of micropipettes for current recordings. From a suspension of purified myelin we have prepared oligolamellar vesicles (mean diameter of 144 nm) using the so-called French pressure system. From this preparation we obtained giant myelin vesicles approximately 10 microns in mean diameter, using a dehydration-rehydration procedure. Qualitative analysis of proteins by sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed no significant loss of any component in these vesicles due to pressure, in comparison with non-vesiculated myelin. A way of preparing giant liposomes of approximately 80-100 microns and proteoliposomes of approximately 30 microns in mean diameter, using the same dehydration-rehydration procedure, is also reported. Reconstitution of purified PLP in giant liposomes was confirmed by fluorescent labeling of PLP and by fluorescence microscopy. The current recordings from these vesicles prove the validity of these methods and provide significant evidence of the existence of ionic channels in myelin membranes and the possibility that PLP functions as a channel. The physiological significance and characterization of these channels remain yet unresolved. These results have a special significance for elucidating the molecular role of myelin in the regulation of neural activity and in the brain ion microenvironment.

Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

2015-10-01

Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

Development of Ionic Liquid Monopropellants for In-Space Propulsion

NASA Technical Reports Server (NTRS)

Blevins, John A.; Osborne, Robin; Drake, Gregory W.

2005-01-01

A family of new, low toxicity, high energy monopropellants is currently being evaluated at NASA Marshall Space Flight Center for in-space rocket engine applications such as reaction control engines. These ionic liquid monopropellants, developed in recent years by the Air Force Research Laboratory, could offer system simplification, less in-flight thermal management, and reduced handling precautions, while increasing propellant energy density as compared to traditional storable in-space propellants such as hydrazine and nitrogen tetroxide. However, challenges exist in identifying ignition schemes for these ionic liquid monopropellants, which are known to burn at much hotter combustion temperatures compared to traditional monopropellants such as hydrazine. The high temperature combustion of these new monopropellants make the use of typical ignition catalyst beds prohibitive since the catalyst cannot withstand the elevated temperatures. Current research efforts are focused on monopropellant ignition and burn rate characterization, parameters that are important in the fundamental understanding of the monopropellant behavior and the eventual design of a thruster. Laboratory studies will be conducted using alternative ignition techniques such as laser-induced spark ignition and hot wire ignition. Ignition delay, defined as the time between the introduction of the ignition source and the first sign of light emission from a developing flame kernel, will be measured using Schlieren visualization. An optically-accessible liquid monopropellant burner will be used to determine propellant burn rate as a function of pressure and initial propellant temperature. The burn rate will be measured via high speed imaging through the chamber s windows.

High Packing Density Unidirectional Arrays of Vertically Aligned Graphene with Enhanced Areal Capacitance for High-Power Micro-Supercapacitors.

PubMed

Zheng, Shuanghao; Li, Zhilin; Wu, Zhong-Shuai; Dong, Yanfeng; Zhou, Feng; Wang, Sen; Fu, Qiang; Sun, Chenglin; Guo, Liwei; Bao, Xinhe

2017-04-25

Interfacial integration of a shape-engineered electrode with a strongly bonded current collector is the key for minimizing both ionic and electronic resistance and then developing high-power supercapacitors. Herein, we demonstrated the construction of high-power micro-supercapacitors (VG-MSCs) based on high-density unidirectional arrays of vertically aligned graphene (VG) nanosheets, derived from a thermally decomposed SiC substrate. The as-grown VG arrays showed a standing basal plane orientation grown on a (0001̅) SiC substrate, tailored thickness (3.5-28 μm), high-density structurally ordering alignment of graphene consisting of 1-5 layers, vertically oriented edges, open intersheet channels, high electrical conductivity (192 S cm -1 ), and strong bonding of the VG edges to the SiC substrate. As a result, the demonstrated VG-MSCs displayed a high areal capacitance of ∼7.3 mF cm -2 and a fast frequency response with a short time constant of 9 ms. Furthermore, VG-MSCs in both an aqueous polymer gel electrolyte and nonaqueous ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate operated well at high scan rates of up to 200 V s -1 . More importantly, VG-MSCs offered a high power density of ∼15 W cm -3 in gel electrolyte and ∼61 W cm -3 in ionic liquid. Therefore, this strategy of producing high-density unidirectional VG nanosheets directly bonded on a SiC current collector demonstrated the feasibility of manufacturing high-power compact supercapacitors.

Probing DNA in nanopores via tunneling: from sequencing to ``quantum'' analogies

NASA Astrophysics Data System (ADS)

di Ventra, Massimiliano

2012-02-01

Fast and low-cost DNA sequencing methods would revolutionize medicine: a person could have his/her full genome sequenced so that drugs could be tailored to his/her specific illnesses; doctors could know in advance patients' likelihood to develop a given ailment; cures to major diseases could be found faster [1]. However, this goal of ``personalized medicine'' is hampered today by the high cost and slow speed of DNA sequencing methods. In this talk, I will discuss the sequencing protocol we suggest which requires the measurement of the distributions of transverse currents during the translocation of single-stranded DNA into nanopores [2-5]. I will support our conclusions with a combination of molecular dynamics simulations coupled to quantum mechanical calculations of electrical current in experimentally realizable systems [2-5]. I will also discuss recent experiments that support these theoretical predictions. In addition, I will show how this relatively unexplored area of research at the interface between solids, liquids, and biomolecules at the nanometer length scale is a fertile ground to study quantum phenomena that have a classical counterpart, such as ionic quasi-particles, ionic ``quantized'' conductance [6,7] and Coulomb blockade [8]. Work supported in part by NIH. [4pt] [1] M. Zwolak, M. Di Ventra, Physical Approaches to DNA Sequencing and Detection, Rev. Mod. Phys. 80, 141 (2008).[0pt] [2] M. Zwolak and M. Di Ventra, Electronic signature of DNA nucleotides via transverse transport, Nano Lett. 5, 421 (2005).[0pt] [3] J. Lagerqvist, M. Zwolak, and M. Di Ventra, Fast DNA sequencing via transverse electronic transport, Nano Lett. 6, 779 (2006).[0pt] [4] J. Lagerqvist, M. Zwolak, and M. Di Ventra, Influence of the environment and probes on rapid DNA sequencing via transverse electronic transport, Biophys. J. 93, 2384 (2007).[0pt] [5] M. Krems, M. Zwolak, Y.V. Pershin, and M. Di Ventra, Effect of noise on DNA sequencing via transverse electronic transport, Biophys. J. 97, 1990, (2009).[0pt] [6] M. Zwolak, J. Lagerqvist, and M. Di Ventra, Ionic conductance quantization in nanopores, Phys. Rev.Lett. 103, 128102 (2009).[0pt] [7] M. Zwolak, J. Wilson, and M. Di Ventra, Dehydration and ionic conductance quantization in nanopores, J. Phys. Cond. Matt. 22 454126 (2011). [0pt] [8] M. Krems and M. Di Ventra, Ionic Coulomb blockade in nanopores arXiv:1103.2749.

F region above Kauai - Measurement, model, modification

NASA Technical Reports Server (NTRS)

Johnson, C. Y.; Sjolander, G. W.; Oran, E. S.; Young, T. R.; Bernhardt, P. A.; Da Rosa, A. V.

1980-01-01

Results of the Lagopedo II experiment conducted from Kauai, Hawaii to investigate the ionospheric modification that occurs when rocket combustion products are introduced into the O(+)-rich F region are presented. The experiment involved the detonation of a chemical explosion in the F2 peak accompanied by rocket-borne measurements of ion composition and electron content in the vicinity of the explosion. The experimental data is found to be in good agreement with the predictions of a model of the nighttime ion densities in the midlatitude laminar ionosphere, with the exception of N2(+) densities before the explosion. H2O(+) and H3O(+) currents produced by considerable H2O outgassing from the rocket are used to determine a H3O(+)/H2O(+) dissociative recombination rate averaging 1.6 to 1.08, depending on model assumptions. At the time of the explosion, an ionic void 1 km in radius is observed, the boundary of which is characterized by a steep gradient in ionic densities. Evidence of variations in the concentrations of ambient ion species, new reactant species and ionic depletion by sweeping is also obtained.

Communication: Stiff and soft nano-environments and the "Octopus Effect" are the crux of ionic liquid structural and dynamical heterogeneity

NASA Astrophysics Data System (ADS)

Daly, Ryan P.; Araque, Juan C.; Margulis, Claudio J.

2017-08-01

In a recent set of articles [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015) and J. C. Araque et al., J. Chem. Phys. 144, 204504 (2016)], we proposed the idea that for small neutral and charged solutes dissolved in ionic liquids, deviation from simple hydrodynamic predictions in translational and rotational dynamics can be explained in terms of diffusion through nano-environments that are stiff (high electrostriction, charge density, and number density) and others that are soft (charge depleted). The current article takes a purely solvent-centric approach in trying to provide molecular detail and intuitive visual understanding of time-dependent local mobility focusing on the most common case of an ionic liquid with well defined polar and apolar nano-domains. We find that at intermediate time scales, apolar regions are fluid, whereas the charge network is much less mobile. Because apolar domains and cationic heads must diffuse as single species, at long time the difference in mobility also necessarily dissipates.

An air-stable Na 3SbS 4 superionic conductor prepared by a rapid and economic synthetic procedure

DOE PAGES

Wang, Hui; Chen, Yan; Hood, Zachary D.; ...

2016-01-01

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Ionic-Liquid-Mediated Extraction and Separation Processes for Bioactive Compounds: Past, Present, and Future Trends.

PubMed

Ventura, Sónia P M; E Silva, Francisca A; Quental, Maria V; Mondal, Dibyendu; Freire, Mara G; Coutinho, João A P

2017-05-24

Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid-liquid extractions, IL-based liquid-liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations.

Application of nonflammable electrolyte with room temperature ionic liquids (RTILs) for lithium-ion cells

NASA Astrophysics Data System (ADS)

Nakagawa, Hiroe; Fujino, Yukiko; Kozono, Suguru; Katayama, Yoshihiro; Nukuda, Toshiyuki; Sakaebe, Hikari; Matsumoto, Hajime; Tatsumi, Kuniaki

A mixture of flammable organic solvent and nonflammable room temperature ionic liquid (RTIL) has been investigated as a new concept electrolyte to improve the safety of lithium-ion cells. This study focused on the use of N-methyl- N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI) as the RTIL for the flame-retardant additive. It was found that a carbon negative electrode, both graphite and hard carbon, could be used with the mixed electrolyte. A 383562-size lithium-ion trial cell made with the mixed electrolyte showed good discharge capacity, which was equivalent to a cell with conventional organic electrolyte up to a discharge current rate of complete discharge in 1 h. Moreover, the mixed electrolyte was observed to be nonflammable at ionic liquid contents of 40 mass% or more. Thus the mixed electrolyte was found to realize both nonflammability and the good discharge performance of lithium-ion cells with carbon negative electrodes. These results indicate that RTILs have potential as a flame-retardant additive for the organic electrolytes used in lithium-ion cells.

Photochemically Powered AgCl Janus Micromotors as a Model System to Understand Ionic Self-Diffusiophoresis.

PubMed

Zhou, Chao; Zhang, H P; Tang, Jinyao; Wang, Wei

2018-03-13

Micromotors are an emerging class of micromachines that could find potential applications in biomedicine, environmental remediation, and microscale self-assembly. Understanding their propulsion mechanisms holds the key to their future development. This is especially true for a popular category of micromotors that are driven by asymmetric surface photochemical reactions. Many of these micromotors release ionic species and are propelled via a mechanism termed "ionic self-diffusiophoresis". However, exactly how it operates remains vague. To address this fundamental yet important issue, we have developed a dielectric-AgCl Janus micromotor that clearly moves away from the AgCl side when exposed to UV or strong visible light. Taking advantage of numerical simulations and acoustic levitation techniques, we have provided tentative explanations for its speed decay over time as well as its directionality. In addition, photoactive AgCl micromotors demonstrate interesting gravitactic behaviors that hint at three-dimensional transport or sensing applications. The current work presents a well-controlled and easily fabricated model system to understand chemically powered micromotors, highlighting the usefulness of acoustic levitation for studying active matter free from the effect of boundaries.

Crew Exploration Vehicle (CEV) Potable Water System Verification Description

NASA Technical Reports Server (NTRS)

Peterson, Laurie; DeVera, Jean; Vega, Leticia; Adam, Nik; Steele, John; Rector, Tony; Gazda, Daniel; Roberts, Michael

2008-01-01

The Crew Exploration Vehicle (CEV), also known as Orion, will ferry a crew of up to six astronauts to the International Space Station (ISS), or a crew of up to four astronauts to the moon. The first launch of CEV is scheduled for approximately 2014. A stored water system on the CEV will supply the crew with potable water for various purposes: drinking and food rehydration, hygiene, medical needs, sublimation, and various contingency situations. The current baseline biocide for the stored water system is ionic silver, similar in composition to the biocide used to maintain quality of the water transferred from the Orbiter to the ISS and stored in Contingency Water Containers (CWCs). In the CEV water system, the ionic silver biocide is expected to be depleted from solution due to ionic silver plating onto the surfaces of the materials within the CEV water system, thus negating its effectiveness as a biocide. Since the biocide depletion is expected to occur within a short amount of time after loading the water into the CEV water tanks at the Kennedy Space Center (KSC), an additional microbial

Ionic-Liquid-Mediated Extraction and Separation Processes for Bioactive Compounds: Past, Present, and Future Trends

PubMed Central

2017-01-01

Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid–liquid extractions, IL-based liquid–liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations. PMID:28151648

Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

NASA Astrophysics Data System (ADS)

Leadbetter, Kirt C.

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price. Advancements of this nonaqueous aluminum plating process have the potential to lead to a novel and competitive commercial aluminum deposition process. In this investigation aluminum electrodeposition from ionic liquid based electrolytes onto steel, copper and magnesium substrates without conversion coatings or strike layers was evaluated in six different ionic liquid based electrolytes in two technical setups. Three of which are commercially available aluminum plating electrolytes, three of which, discussed in literature were created on site by research personnel in the laboratory. The three commercially available electrolytes were: 1-Butyl-3-methylimidazolium chloride ([BMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, 1-Ethyl-3-methylimidazolium chloride ([EMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, and BasionicsTM AL-02, an aluminum plating electrolyte containing [EMIm]Cl * 1.5 AlCl3 with additives from BASF. The three electrolytes created on site were based on the 1-ethyl-3-methylimidazolium chloride ionic liquid with added 1.5 AlCl3 and one with added sodium dodecyl sulfate. Small scale plating tests in a 25-mL plating cell were conducted to provide a comparative analysis of the six different electrolytes considered. From these investigations, two were chosen to be evaluated in a larger 1-liter plating cell; designed and constructed to provide a more realistic evaluation of plating parameters with selected electrolytes to better portray industrial electroplating conditions. The effect of current density (10-40 mA/cm 2), temperature (30-90° Celsius) and plating bath agitation on current efficiency, corrosion resistance by the ASTM B117 method, adhesion, microstructure, and chemical composition (evaluated with energy-dispersive x-ray spectroscopy) of the plated Al-layer was explored in both the 25-mL and 1-L plating cell investigations. In addition development of pre- and post-treatment processes for the metal substrates was attempted. While previous investigations focused on one or two of these topics, this research seeks to investigate all discussed phenomena and characteristics. Additionally, there is little research that reports on the adhesion performance of aluminum coatings from ionic liquids. Also, corrosion investigations are limited to all but a few publications. So too, the deposition of aluminum in a larger, more realistic plating cell has never been thoroughly investigated. This is key if a practical application of the technology is ever to be realized. In sum, correlations were drawn between electrolyte, current density, temperature and bath agitation with quality and characteristic of electrodeposited aluminum layers. The overriding goal to create an acceptably competitive aluminum coating process to replace cadmium and compete with other commercial aluminum deposition processes was not successful. Competitiveness was evaluated as per the discussed characteristics and so also, by a comparison to physical samples created in a more realistic plating cell to AlumiPlate aluminum coatings.

At the Crossroads of Nanotoxicology: Past Achievements and Current Challenges

DTIC Science & Technology

2015-01-01

rates of ionic dissolution, improving in vitro to in vivo predictive efficiencies, and establishing safety exposure limits. This Review will discuss...Oberdörster et al., 2005a), which drove the focus of in vitro and in vivo model selection to accommodate these areas of higher NM exposure. Most...Accordingly, a current challenge is the design of simple, in vitro models that reliably predict in vivo effects following a NM challenge. In order

Advances in the analysis of biological samples using ionic liquids.

PubMed

Clark, Kevin D; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-02-12

Ionic liquids are a class of solvents and materials that hold great promise in bioanalytical chemistry. Task-specific ionic liquids have recently been designed for the selective extraction, separation, and detection of proteins, peptides, nucleic acids, and other physiologically relevant analytes from complex biological samples. To facilitate rapid bioanalysis, ionic liquids have been integrated in miniaturized and automated procedures. Bioanalytical separations have also benefited from the modification of nonspecific magnetic materials with ionic liquids or the implementation of ionic liquids with inherent magnetic properties. Furthermore, the direct detection of the extracted molecules in the analytical instrument has been demonstrated with structurally tuned ionic liquids and magnetic ionic liquids, providing a significant advantage in the analysis of low-abundance analytes. This article gives an overview of these advances that involve the application of ionic liquids and derivatives in bioanalysis. Graphical abstract Ionic liquids, magnetic ionic liquids, and ionic liquid-based sorbents are increasing the speed, selectivity, and sensitivity in the analysis of biological samples.

Effect of ethanol at clinically relevant concentrations on atrial inward rectifier potassium current sensitive to acetylcholine.

PubMed

Bébarová, Markéta; Matejovič, Peter; Pásek, Michal; Hořáková, Zuzana; Hošek, Jan; Šimurdová, Milena; Šimurda, Jiří

2016-10-01

Alcohol intoxication tends to induce arrhythmias, most often the atrial fibrillation. To elucidate arrhythmogenic mechanisms related to alcohol consumption, the effect of ethanol on main components of the ionic membrane current is investigated step by step. Considering limited knowledge, we aimed to examine the effect of clinically relevant concentrations of ethanol (0.8-80 mM) on acetylcholine-sensitive inward rectifier potassium current I K(Ach). Experiments were performed by the whole-cell patch clamp technique at 23 ± 1 °C on isolated rat and guinea-pig atrial myocytes, and on expressed human Kir3.1/3.4 channels. Ethanol induced changes of I K(Ach) in the whole range of concentrations applied; the effect was not voltage dependent. The constitutively active component of I K(Ach) was significantly increased by ethanol with the maximum effect (an increase by ∼100 %) between 8 and 20 mM. The changes were comparable in rat and guinea-pig atrial myocytes and also in expressed human Kir3.1/3.4 channels (i.e., structural correlate of I K(Ach)). In the case of the acetylcholine-induced component of I K(Ach), a dual ethanol effect was apparent with a striking heterogeneity of changes in individual cells. The effect correlated with the current magnitude in control: the current was increased by eth-anol in the cells showing small current in control and vice versa. The average effect peaked at 20 mM ethanol (an increase of the current by ∼20 %). Observed changes of action potential duration agreed well with the voltage clamp data. Ethanol significantly affected both components of I K(Ach) even in concentrations corresponding to light alcohol consumption.

Ionic liquids as novel solvents for ionic polymer transducers

NASA Astrophysics Data System (ADS)

Bennett, Matthew D.; Leo, Donald J.

2004-07-01

The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

Passivation effects on quantum dots prepared by successive ionic layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Dai, Qilin; Maloney, Scott; Chen, Weimin; Poudyal, Uma; Wang, Wenyong

2016-06-01

ZnS is typically used to passivate semiconductor quantum dots (QDs) prepared by the successive ionic layer adsorption and reaction (SILAR) method for solar cell applications, while for colloidal QDs, organic ligands are usually used for this passivation purpose. In this study we utilized oleylamine and oleic acid ligands, besides ZnS, to passivate QDs prepared by the SILAR approach, and investigated their effects on the incident photon-to-current efficiency (IPCE) performance of the solar cells. It was observed that oleylamine passivation decreased device performance, while oleic acid passivation improved the IPCE of the cells. Redshift of the IPCE onset wavelength was also observed after oleic acid coating, which was attributed to the delocalization of excitons in the CdS QDs.

On the dielectric conductivity of molecular ionic liquids.

PubMed

Schröder, Christian; Steinhauser, Othmar

2009-09-21

The contribution of the conductivity to the spectrum of the generalized dielectric constant or susceptibility of molecular ionic liquids is analyzed, both in theoretical terms and computationally by means of molecular dynamics simulation of the concrete system 1-ethyl-3-methyl-imidazolium dicyanoamide at 300 K. As a central quantity the simulated current autocorrelation function is modeled by a carefully designed fit function. This not only gives a satisfactory numerical representation but yields the correct conductivity upon integration. In addition the fit function can be Fourier-Laplace transformed analytically. Both, the real and imaginary parts of the transform show expected behavior, in particular, the right limits for zero frequency. This altogether demonstrates that the components of the fit function are of physical relevance.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

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

Asadi, M.; Kim, K.; Liu, C.

2016-07-28

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform thatmore » concurrently oxidized water in the absence of any external potential.« less

Ewald Summation Approach to Potential Models of Aqueous Electrolytes Involving Gaussian Charges and Induced Dipoles: Formal and Simulation Results

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2014-11-01

We present a detailed derivation of the complete set of expressions required for the implementation of an Ewald summation approach to handle the long-range electrostatic interactions of polar and ionic model systems involving Gaussian charges and induced dipole moments with a particular application to the isobaricisothermal molecular dynamics simulation of our Gaussian Charge Polarizable (GCP) water model and its extension to aqueous electrolytes solutions. The set comprises the individual components of the potential energy, electrostatic potential, electrostatic field and gradient, the electrostatic force and the corresponding virial. Moreover, we show how the derived expressions converge to known point-based electrostatic counterpartsmore » when the parameters, defining the Gaussian charge and induced-dipole distributions, are extrapolated to their limiting point values. Finally, we illustrate the Ewald implementation against the current reaction field approach by isothermal-isobaric molecular dynamics of ambient GCP water for which we compared the outcomes of the thermodynamic, microstructural, and polarization behavior.« less

1-Butyl-3-Methyl Imidazolium-based Ionic Liquids Explored as Potential Solvents for Lipid Processing

USDA-ARS?s Scientific Manuscript database

Due to global environmental concerns, there is increasing interest in replacing the volatile solvents currently used to process commodity plant lipids. Room-temperature molten salts are one type of media receiving great attention as a possible replacement of the typical organic solvent. Molten sal...

Cardiac Electrophysiology: Normal and Ischemic Ionic Currents and the ECG

ERIC Educational Resources Information Center

Klabunde, Richard E.

2017-01-01

Basic cardiac electrophysiology is foundational to understanding normal cardiac function in terms of rate and rhythm and initiation of cardiac muscle contraction. The primary clinical tool for assessing cardiac electrical events is the electrocardiogram (ECG), which provides global and regional information on rate, rhythm, and electrical…

Extending the Diffuse Layer Model of Surface Acidity Constant Behavior: IV. Diffuse Layer Charge/Potential Relationships

EPA Science Inventory

Most current electrostatic surface complexation models describing ionic binding at the particle/water interface rely on the use of Poisson - Boltzmann (PB) theory for relating diffuse layer charge densities to diffuse layer electrostatic potentials. PB theory is known to contain ...

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform.

PubMed

Sun, Gongchen; Senapati, Satyajyoti; Chang, Hsueh-Chia

2016-04-07

A microfluidic ion exchange membrane hybrid chip is fabricated using polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (>100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems.

Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

PubMed

Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

2016-04-04

Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffuse-charge dynamics of ionic liquids in electrochemical systems.

PubMed

Zhao, Hui

2011-11-01

We employ a continuum theory of solvent-free ionic liquids accounting for both short-range electrostatic correlations and steric effects (finite ion size) [Bazant et al., Phys. Rev. Lett. 106, 046102 (2011)] to study the response of a model microelectrochemical cell to a step voltage. The model problem consists of a 1-1 symmetric ionic liquid between two parallel blocking electrodes, neglecting any transverse transport phenomena. Matched asymptotic expansions in the limit of thin double layers are applied to analyze the resulting one-dimensional equations and study the overall charge-time relation in the weakly nonlinear regime. One important conclusion is that our simple scaling analysis suggests that the length scale √(λ*(D)l*(c)) accurately characterizes the double-layer structure of ionic liquids with strong electrostatic correlations where l*(c) is the electrostatic correlation length (in contrast, the Debye screening length λ*(D) is the primary double-layer length for electrolytes) and the response time of λ(D)(*3/2)L*/(D*l(c)(1/2)) (not λ*(D)L*/D* that is the primary charging time of electrolytes) is the correct charging time scale of ionic liquids with strong electrostatic correlations where D* is the diffusivity and L* is the separation length of the cell. With these two new scales, data of both electric potential versus distance from the electrode and the total diffuse charge versus time collapse onto each individual master curve in the presence of strong electrostatic correlations. In addition, the dependance of the total diffuse charge on steric effects, short-range correlations, and driving voltages is thoroughly examined. The results from the asymptotic analysis are compared favorably with those from full numerical simulations. Finally, the absorption of excess salt by the double layer creates a depletion region outside the double layer. Such salt depletion may bring a correction to the leading order terms and break down the weakly nonlinear analysis. A criterion which justifies the weakly nonlinear analysis is verified with numerical simulations.

Non-ionic iodinated contrast media related immediate reactions: A mechanism study of 27 patients.

PubMed

Zhai, Liqin; Guo, Xiangjie; Zhang, Haoyue; Jin, Qianqian; Zeng, Qiang; Tang, Xiaoxian; Gao, Cairong

2017-01-01

The underlying mechanism of non-ionic iodinated contrast media-related immediate reactions was evaluated in this study. Patients presenting at least grade II immediate reactions after non-ionic iodinated contrast media injection were enrolled. Basophil activation was evaluated by flow cytometry. The plasma concentration of human terminal complement complex SC5b-9, as well as concentrations of serum chymase, tryptase, human mast cell carboxypeptidase A3, human prostaglandin D2, and total IgE were measured by enzyme-linked immunosorbent assay. The basophil activation percentage was significantly higher in the study group than in the control group (17.94±21.06% vs 3.45±1.49%). The plasma concentration of human terminal complement complex SC5b-9 and concentrations of serum chymase, human mast cell carboxypeptidase A3, prostaglandin D2, tryptase, and total IgE were also significantly increased (236.99±318.21 vs 49.70±30.41ng/mL, 0.41±0.49 vs 0.09±0.06ng/mL, 1.17±0.67 vs 0.30±0.17ng/mL, 203.52±137.27 vs 102.28±48.72pg/mL, 3.81±0.22 vs 2.70±0.16ng/mL, 102.00±51.84 vs 19.97±2.75ng/mL, respectively). Both mast cells and basophils were activated in non-ionic iodinated contrast media to mediate immediate hypersensitivity, and mast cells may be involved. Different mechanisms, including IgE-dependent, complement-dependent, and direct membrane effects, contributed to mast cell and basophil activation. Individual patients may use a single or combined mechanism involving single or combined mast cells and basophils. Immediate reactions following non-ionic iodinated contrast media injection may be a mechanically heterogenous disease. Copyright © 2016. Published by Elsevier B.V.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

DOE PAGES

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung; ...

2018-05-24

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

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

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Porous ionic liquids: synthesis and application.

PubMed

Zhang, Shiguo; Dokko, Kaoru; Watanabe, Masayoshi

2015-07-15

Solidification of fluidic ionic liquids into porous materials yields porous ionic networks that combine the unique characteristics of ionic liquids with the common features of polymers and porous materials. This minireview reports the most recent advances in the design of porous ionic liquids. A summary of the synthesis of ordered and disordered porous ionic liquid-based nanoparticles or membranes with or without templates is provided, together with the new concept of room temperature porous ionic liquids. As a versatile platform for functional materials, porous ionic liquids have shown widespread applications in catalysis, adsorption, sensing, actuation, etc. This new research direction towards ionic liquids chemistry is still in its early stages but has great potential.

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform†

PubMed Central

Sun, Gongchen; Senapati, Satyajyoti

2016-01-01

A microfluidic-ion exchange membrane hybrid chip is fabricated by polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (> 100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems. PMID:26960551

Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions

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

Rinne, Klaus F.; Netz, Roland R.; Gekle, Stephan

2014-12-07

Using extensive equilibrium molecular dynamics simulations we determine the dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-specific and concentration-dependent shifts of the static dielectric constants and the dielectric relaxation times match experimental results very well, which serves as a validation of the classical and non-polarizable ionic force fields used. The purely ionic contribution to the dielectric response is negligible, but determines the conductivity of the salt solutions. The ion-water cross correlation contribution is negative and reduces the total dielectric response by about 5%-10% for 1 M solutions. The dominating water dielectric response is decomposed into differentmore » water solvation shells and ion-pair configurations, by this the spectral blue shift and the dielectric decrement of salt solutions with increasing salt concentration is demonstrated to be primarily caused by first-solvation shell water. With rising salt concentration the simulated spectra show more pronounced deviations from a single-Debye form and can be well described by a Cole-Cole fit, in quantitative agreement with experiments. Our spectral decomposition into ionic and different water solvation shell contributions does not render the individual contributions more Debye-like, this suggests the non-Debye-like character of the dielectric spectra of salt solutions not to be due to the superposition of different elementary relaxation processes with different relaxation times. Rather, the non-Debye-like character is likely to be an inherent spectral signature of solvation water around ions.« less

Ionic liquid-assisted synthesis of highly dispersive bowknot-like ZnO microrods for photocatalytic applications

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Zhou, Yuming; Zhang, Chao; Sheng, Xiaoli; Fang, Jiasheng; Zhang, Mingyu; Yang, Yong

2017-04-01

Here we present a facile method for the preparation of highly dispersive ZnO materials by using ionic liquid 1-methyl-3-[3‧-(trimethoxysilyl) propyl] imidazolium chloride as the template. The influence of ionic liquid concentration and calcined atmosphere on the photoactivity is studied. The samples were characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), scanning electron microscope (SEM), N2 gas sorption and ultraviolet-visible diffuse reflectance spectroscopy. The results showed that the as-fabricated ZnO materials consisted of individual microrods with self-assembled bowknot-like architecture whose size was about 1 μm. The formation mechanism of the bowknot-like ZnO materials which is based on the self-assembly of ionic liquid is tentatively elucidated. Moreover, the ZnO-2.6N sample exhibited the higher activity for the photodegradation of MB than the photodegradation of MO and RhB. Furthermore, it was found that the ZnO materials calcined under air atmosphere showed the better photocatalytic activities than that of samples calcined under nitrogen atmosphere in the degradation of methylene blue (MB) under UV irradiation. And the special structure, surface area, adsorption capability of dye, the separation rate of photogenerated electron-hole pairs and band gap had effects on the photocatalytic activity of ZnO photocatalysts. O2rad - was the main active species for the photocatalytic degradation of MB. It is valuable to develop this facile route preparing the highly dispersive bowknot-like ZnO materials and the ZnO materials can be beneficial for environmental protection.

Characterization of Ocular Iontophoretic Drug Transport of Ionic and Non-ionic Compounds in Isolated Rabbit Cornea and Conjunctiva.

PubMed

Sekijima, Hidehisa; Ehara, Junya; Hanabata, Yusuke; Suzuki, Takumi; Kimura, Soichiro; Lee, Vincent H L; Morimoto, Yasunori; Ueda, Hideo

2016-06-01

Ocular iontophoresis (IP) in isolated rabbit cornea and conjunctiva was examined in terms of transport enhancement, tissue viability and integrity using electrophysiological parameters by the Ussing-type chamber technique. Lidocaine hydrochloride (LC, a cationic compound), sodium benzoate (BA, anionic compound), and fluorescein isothiocyanate labeled dextran (molecular weight 4400 Da, FD-4, hydrophilic large compound) were used as model permeants. Direct electric current was applied at 0.5-5.0 mA/cm(2) for the cornea and 0.5-20 mA/cm(2) for the conjunctiva for 30 min. LC and BA fluxes across the cornea and conjunctiva were significantly increased by the application of electric current up to 2.3- and 2.5-fold and 4.0- and 3.4-fold, respectively, and returned to their baseline level on stopping the current. Furthermore, a much higher increase by IP application was obtained for the FD-4 transport. The increased FD-4 flux in the conjunctiva returned to baseline on stopping the current, whereas the flux in the cornea was sustained at a higher level after stopping the current. The transepithelial electric resistance of the cornea and conjunctiva was lowered by electric current application but fully recovered after stopping the current up to 2.0 mA/cm(2) for the cornea and 10 mA/cm(2) for the conjunctiva, suggesting that the corneal and conjunctival viability and integrity are maintained even after application of these current densities. These results indicate that ocular IP may be a useful non-invasive technique to achieve drug delivery of hydrophilic large molecules into the eyes.

Reduction of I(Ca,L) and I(to1) density in hypertrophied right ventricular cells by simulated high altitude in adult rats.

PubMed

Chouabe, C; Espinosa, L; Megas, P; Chakir, A; Rougier, O; Freminet, A; Bonvallet, R

1997-01-01

The present paper describes the effect of a simulated hypobaric condition (at the altitude of 4500 m) on morphological characteristics and on some ionic currents in ventricular cells of adult rats. According to current data, chronic high-altitude exposure led to mild right ventricular hypertrophy. Increase in right ventricular weight appeared to be due wholly or partly to an enlargement of myocytes. The whole-cell patch-clamp technique was used and this confirmed, by cell capacitance measurement, that chronic high-altitude exposure induced an increase in the size of the right ventricular cells. Hypertrophied cells showed prolongation of action potential (AP). Four ionic currents, playing a role along with many others in the precise balance of inward and outward currents that control the duration of cardiac AP, were investigated. We report a significant decrease in the transient outward (I(to1)) and in the L-type calcium current (I(Ca,L)) densities while there was no significant difference in the delayed rectifier current (I(K)) or in the inward rectifier current (I(K1)) densities in hypertrophied right ventricular cells compared to control cells. At a given potential the decrease in I(to 1) density was relatively more important than the decrease in I(Ca,L) density. In both cell types, all the currents displayed the same voltage dependence. The inactivation kinetics of I(to 1) and I(Ca,L) or the steady-state activation and inactivation relationships were not significantly modified by chronic high-altitude exposure. We conclude that chronic high-altitude exposure induced true right ventricular myocyte hypertrophy and that the decrease in I(to 1) density might account for the lengthened action potential, or have a partial effect.

Electrical properties associated with wide intercellular clefts in rabbit Purkinje fibres.

PubMed Central

Colatsky, T J; Tsien, R W

1979-01-01

1. Rabbit Purkinje fibres were studied using micro-electrode recordings of electrical activity or a two-micro-electrode voltage clamp. Previous morphological work had suggested that these preparations offer structural advantages for the analysis of ionic permeability mechanisms. 2. Viable preparations could be obtained consistently by exposure to a K glutamate Tyrode solution during excision and recovery. In NaCl Tyrode solution, the action potential showed a large overshoot and fully developed plateau, but no pacemaker depolarization at negative potentials. 3. The passive electrical properties were consistent with morphological evidence for the accessibility of cleft membranes within the cell bundle. Electrotonic responses to intracellular current steps showed the behaviour expected for a simple leaky capacitative cable. Capacitative current transients under voltage clamp were changed very little by an eightfold reduction in the external solution conductivity. 4. Slow current changes attributable to K depletion were small compared to those found in other cardiac preparations. The amount of depletion was close to that predicted by a cleft model which assumed free K diffusion in 1 micron clefts. 5. Step depolarizations over the plateau range of potentials evoked a slow inward current which was resistant to tetrodotoxin but blocked by D600. 6. Strong depolarizations to potentials near 0 mV elicited a transient outward current and a slowly activating late outward current. Both components resembled currents found in sheep or calf Purkinje fibres. 7. These experiments support previous interpretations of slow plateau currents in terms of genuine permeability changes. The rabbit Purkinje fibre may allow various ionic channels to be studied with relatively little interference from radial non-uniformities in membrane potential or ion concentration. Images Fig. 7 PMID:469754

The electrical properties of auditory hair cells in the frog amphibian papilla.

PubMed

Smotherman, M S; Narins, P M

1999-07-01

The amphibian papilla (AP) is the principal auditory organ of the frog. Anatomical and neurophysiological evidence suggests that this hearing organ utilizes both mechanical and electrical (hair cell-based) frequency tuning mechanisms, yet relatively little is known about the electrophysiology of AP hair cells. Using the whole-cell patch-clamp technique, we have investigated the electrical properties and ionic currents of isolated hair cells along the rostrocaudal axis of the AP. Electrical resonances were observed in the voltage response of hair cells harvested from the rostral and medial, but not caudal, regions of the AP. Two ionic currents, ICa and IK(Ca), were observed in every hair cell; however, their amplitudes varied substantially along the epithelium. Only rostral hair cells exhibited an inactivating potassium current (IA), whereas an inwardly rectifying potassium current (IK1) was identified only in caudal AP hair cells. Electrically tuned hair cells exhibited resonant frequencies from 50 to 375 Hz, which correlated well with hair cell position and the tonotopic organization of the papilla. Variations in the kinetics of the outward current contribute substantially to the determination of resonant frequency. ICa and IK(Ca) amplitudes increased with resonant frequency, reducing the membrane time constant with increasing resonant frequency. We conclude that a tonotopically organized hair cell substrate exists to support electrical tuning in the rostromedial region of the frog amphibian papilla and that the cellular mechanisms for frequency determination are very similar to those reported for another electrically tuned auditory organ, the turtle basilar papilla.

How to interpret current-voltage relationships of blocking grain boundaries in oxygen ionic conductors.

PubMed

Kim, Seong K; Khodorov, Sergey; Chen, Chien-Ting; Kim, Sangtae; Lubomirsky, Igor

2013-06-14

A new model based on a linear diffusion equation is proposed to explain the current-voltage characteristics of blocking grain boundaries in Y-doped CeO2 in particular. One can also expect that the model can be applicable to the ionic conductors with blocking grain boundaries, in general. The model considers an infinitely long chain of identical grains separated by grain boundaries, which are treated as regions in which depletion layers of mobile ions are formed due to trapping of immobile charges that do not depend on the applied voltage as well as temperature. The model assumes that (1) the grain boundaries do not represent physical blocking layers, which implies that if there is a second phase at the grain boundaries, then it is too thin to impede ion diffusion and (2) the ions follow Boltzmann distribution throughout the materials. Despite its simplicity, the model successfully reproduces the "power law": current proportional to voltage power n and illustrated with the experimental example of Y-doped ceria. The model also correctly predicts that the product nT, where T is the temperature in K, is constant and is proportional to the grain boundary potential as long as the charge at the grain boundaries remains trapped. The latter allows its direct determination from the current-voltage characteristics and promises considerable simplification in the analysis of the electrical characteristics of the grain boundaries with respect to the models currently in use.

Gating current studies reveal both intra- and extracellular cation modulation of K+ channel deactivation

PubMed Central

Wang, Zhuren; Zhang, Xue; Fedida, David

1999-01-01

The presence of permeant ions can modulate the rate of gating charge return in wild-type human heart K+ (hKv1.5) channels. Here we employ gating current measurements in a non-conducting mutant, W472F, of the hKv1.5 channel to investigate how different cations can modulate charge return and whether the actions can be specifically localized at the internal as well as the external mouth of the channel pore. Intracellular cations were effective at accelerating charge return in the sequence Cs+ > Rb+ > K+ > Na+ > NMG+. Extracellular cations accelerated charge return with the selectivity sequence Cs+ > Rb+ > Na+ = NMG+. Intracellular and extracellular cation actions were of relatively low affinity. The Kd for preventing slowing of the time constant of the off-gating current decay (τoff) was 20.2 mM for intracellular Cs+ (Csi+) and 358 mM for extracellular Cs+ (Cso+). Both intracellular and extracellular cations can regulate the rate of charge return during deactivation of hKv1.5, but intracellular cations are more effective. We suggest that ion crystal radius is an important determinant of this action, with larger ions preventing slowing more effectively. Important parallels exist with cation-dependent modulation of slow inactivation of ionic currents in this channel. However, further experiments are required to understand the exact relationship between acceleration of charge return and the slowing of inactivation of ionic currents by cations. PMID:10050001

Mean-Field Description of Ionic Size Effects with Non-Uniform Ionic Sizes: A Numerical Approach

PubMed Central

Zhou, Shenggao; Wang, Zhongming; Li, Bo

2013-01-01

Ionic size effects are significant in many biological systems. Mean-field descriptions of such effects can be efficient but also challenging. When ionic sizes are different, explicit formulas in such descriptions are not available for the dependence of the ionic concentrations on the electrostatic potential, i.e., there is no explicit, Boltzmann type distributions. This work begins with a variational formulation of the continuum electrostatics of an ionic solution with such non-uniform ionic sizes as well as multiple ionic valences. An augmented Lagrange multiplier method is then developed and implemented to numerically solve the underlying constrained optimization problem. The method is shown to be accurate and efficient, and is applied to ionic systems with non-uniform ionic sizes such as the sodium chloride solution. Extensive numerical tests demonstrate that the mean-field model and numerical method capture qualitatively some significant ionic size effects, particularly those for multivalent ionic solutions, such as the stratification of multivalent counterions near a charged surface. The ionic valence-to-volume ratio is found to be the key physical parameter in the stratification of concentrations. All these are not well described by the classical Poisson–Boltzmann theory, or the generalized Poisson–Boltzmann theory that treats uniform ionic sizes. Finally, various issues such as the close packing, limitation of the continuum model, and generalization of this work to molecular solvation are discussed. PMID:21929014

Electrode-electrolyte interface model of tripolar concentric ring electrode and electrode paste.

PubMed

Nasrollaholhosseini, Seyed Hadi; Steele, Preston; Besio, Walter G

2016-08-01

Electrodes are used to transform ionic currents to electrical currents in biological systems. Modeling the electrode-electrolyte interface could help to optimize the performance of the electrode interface to achieve higher signal to noise ratios. There are previous reports of accurate models for single-element biomedical electrodes. In this paper we develop a model for the electrode-electrolyte interface for tripolar concentric ring electrodes (TCRE) that are used to record brain signals.

Functionalized ionic liquids and their applications

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

Hariprakasha, Humcha Krishnamurthy; Rangan, Krishnaswamy Kasthuri; Sudarshan, Tirumalai Srinivas

2018-01-16

Disclosure of functionalized ionic liquids. Use of disclosed ionic liquids as solvent for carbon dioxide. Use of disclosed ionic liquids as flame retardant. Use of disclosed ionic liquids for coating fabric to obtain flame retardant fabric.

Ionic currents and charge movements in organ-cultured rat skeletal muscle.

PubMed

Hollingworth, S; Marshall, M W; Robson, E

1984-12-01

The middle of the fibre voltage-clamp technique was used to measure ionic currents and non-linear charge movements in intact, organ-cultured (in vitro denervated) mammalian fast-twitch (rat extensor digitorum longus) muscle fibres. Muscle fibres organ cultured for 4 days can be used as electrophysiological and morphological models for muscles in vivo denervated for the same length of time. Sodium currents in organ-cultured muscle fibres are similar to innervated fibres except that in the temperature range 0-20 degrees C (a) in the steady state, the voltage distribution of inactivation in cultured fibres is shifted negatively some 20 mV; (b) at the same temperature and membrane potential, the time constant of inactivation in cultured fibres is about twice that of innervated fibres. Potassium currents in innervated and cultured fibres at 15 degrees C can be fitted with the Hodgkin-Huxley n variable raised to the second power. Despite the large range we would estimate that the maximum value of the steady-state potassium conductance of cultured fibres is about one-half that of innervated fibres. The estimated maximum amount of charge moved in cultured fibre is about one-third that in innervated fibres. Compared to innervated fibres, culturing doubles the kinetics of the decay phase of charge movement. The possibility of a negative shift of the voltage distribution of charge movements in cultured fibres is discussed.

FROM THE HISTORY OF PHYSICS: Electrolysis and surface phenomena. To the bicentenary of Volta's publication on the first direct-current source

NASA Astrophysics Data System (ADS)

Gokhshtein, Aleksandr Ya

2000-07-01

The development of knowledge about electric current, potential, and the conversion of energy at the interface between electronic- and ionic-conductivity phases is briefly reviewed. Although soon after its discovery it was realized that electric current is the motion of charged particles, the double-layer field promoting charge transfer through the interface was considered for a long time to be as uniform as in a capacitor. One-dimensional ion discharge theory failed to explain the observed dependence of the current on the potential jump across the interface. The spatial segmentation of energy in the double layer due to the quantum evolution of the layer's periphery puts a limit on the charge transfer work the field may perform locally, and creates conditions for the ionic atmosphere being spontaneously compressed after the critical potential jump has been reached. A discrete interchange of states also occurs due to the adsorption of discharged particles and corresponds to the consecutive exclusion of the d-wave function nodes of metal surface atoms, the exclusion manifesting itself in the larger longitudinal and smaller lateral sizes of the atomic orbital. The elastic extension of the metal surface reduces the d-function overlap thus intensifying adsorption. Advances in experimentation, in particular new techniques capable of detecting alternating surface tension of solids, enabled these and some other phenomena to be observed.

Effect of electrical coupling on ionic current and synaptic potential measurements.

PubMed

Rabbah, Pascale; Golowasch, Jorge; Nadim, Farzan

2005-07-01

Recent studies have found electrical coupling to be more ubiquitous than previously thought, and coupling through gap junctions is known to play a crucial role in neuronal function and network output. In particular, current spread through gap junctions may affect the activation of voltage-dependent conductances as well as chemical synaptic release. Using voltage-clamp recordings of two strongly electrically coupled neurons of the lobster stomatogastric ganglion and conductance-based models of these neurons, we identified effects of electrical coupling on the measurement of leak and voltage-gated outward currents, as well as synaptic potentials. Experimental measurements showed that both leak and voltage-gated outward currents are recruited by gap junctions from neurons coupled to the clamped cell. Nevertheless, in spite of the strong coupling between these neurons, the errors made in estimating voltage-gated conductance parameters were relatively minor (<10%). Thus in many cases isolation of coupled neurons may not be required if a small degree of measurement error of the voltage-gated currents or the synaptic potentials is acceptable. Modeling results show, however, that such errors may be as high as 20% if the gap-junction position is near the recording site or as high as 90% when measuring smaller voltage-gated ionic currents. Paradoxically, improved space clamp increases the errors arising from electrical coupling because voltage control across gap junctions is poor for even the highest realistic coupling conductances. Furthermore, the common procedure of leak subtraction can add an extra error to the conductance measurement, the sign of which depends on the maximal conductance.

Electrophysiological mechanisms of sophocarpine as a potential antiarrhythmic agent.

PubMed

Yang, Zhi-fang; Li, Ci-zhen; Wang, Wei; Chen, Ying-min; Zhang, Ying; Liu, Yuan-mou; Wang, Hong-wei

2011-03-01

To examine the electrophysiological effects of sophocarpine on action potentials (AP) and ionic currents of cardiac myocytes and to compare some of these effects with those of amiodarone. Langendorff perfusion set-up was used in isolated guinea pig heart, and responses to sophocarpine were monitored using electrocardiograph. Conventional microelectrode, voltage clamp technique and perforated patch were employed to record fast response AP (fAP), slow response AP (sAP) and ionic currents in guinea pig papillary muscle or rabbit sinus node cells. Tachyarrhythmia produced by isoprenaline (15 μmol/L) could be reversed by sophocarpine (300 μmol/L). Sophocarpine (10 μmol/L) decreased the amplitude by 4.0%, maximal depolarization velocity (V(max)) of the fAP by 24.4%, and Na(+) current (I(Na)) by 18.0%, while it prolonged the effective refractory period (ERP) by 21.1%. The same concentration of sophocarpine could also decrease the amplitude and V(max) of the sAP, by 26.8% and 25.7%, respectively, and attenuated the Ca(2+) current (I(CaL)) and the K(+) tail current substantially. Comparison of sophocarpine with amiodarone demonstrated that both prolonged the duration and the ERP of fAP and sAP, both decreased the amplitude and V(max) of the fAP and sAP, and both slowed the automatic heart rate. Sophocarpine could reverse isoprenaline-induced arrhythmia and inhibit I(Na), I(CaL), and I(Kr) currents. The electrophysiological effects of sophocarpine are similar to those of amiodarone, which might be regarded as a prospective antiarrhythmic agent.

Bucky gel actuators optimization towards haptic applications

NASA Astrophysics Data System (ADS)

Bubak, Grzegorz; Ansaldo, Alberto; Ceseracciu, Luca; Hata, Kenji; Ricci, Davide

2014-03-01

An ideal plastic actuator for haptic applications should generate a relatively large displacement (minimum 0.2-0.6 mm, force (~50 mN/cm2) and a fast actuation response to the applied voltage. Although many different types of flexible, plastic actuators based on electroactive polymers (EAP) are currently under investigation, the ionic EAPs are the only ones that can be operated at low voltage. This property makes them suitable for applications that require inherently safe actuators. Among the ionic EAPs, bucky gel based actuators are very promising. Bucky gel is a physical gel made by grounding imidazolium ionic liquids with carbon nanotubes, which can then be incorporated in a polymeric composite matrix to prepare the active electrode layers of linear and bending actuators. Anyhow, many conflicting factors have to be balanced to obtain required performance. In order to produce high force a large stiffness is preferable but this limits the displacement. Moreover, the bigger the active electrode the larger the force. However the thicker an actuator is, the slower the charging process becomes (it is diffusion limited). In order to increase the charging speed a thin electrolyte would be desirable, but this increases the probability of pinholes and device failure. In this paper we will present how different approaches in electrolyte and electrode preparation influence actuator performance and properties taking particularly into account the device ionic conductivity (which influences the charging speed) and the electrode surface resistance (which influences both the recruitment of the whole actuator length and its speed).

Nanoparticles in ionic liquids: interactions and organization.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2015-07-28

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

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

Yao, Juan; Zhou, Yufan; Sui, Xiao

The identification of a number of mass peaks in the switchable ionic liquid (SWIL) observed in ToF-SIMS is updated based on the most likely chemical formation pathways. The revised identification better reflects the chemical interactions in the SWIL consisting of DBU, 1-hexanol and CO2. A companion paper illustrates the formation mechanism of these updated species is currently under review.

Toward developing long-life water quality sensors for the ISS using planar REDOX and conductivity sensors

NASA Technical Reports Server (NTRS)

Buehler, M. G.; Kuhlman, G. M.; Keymeulen, D.; Myung, N.; Kounaves, S. P.

2003-01-01

REDOX and conductivity sensors are metal electrodes that are used to detect ionic species in solution by measuring the electrochemical cell current as the voltage is scanned. This paper describes the construction of the sensors, the potentiostat electronics, the measurement methodology, and applications to water quality measurements.

Process for electrospinning chitin fibers from chitinous biomass solution

DOEpatents

Swatloski, Richard P.; Barber, Patrick S.; Opichka, Terrance; Bonner, Jonathan R.; Gurau, Gabriela; Griggs, Christopher Scott; Rogers, Robin D.

2017-06-20

Disclosed are methods for electrospinning chitinous biomass solution to form chitin fibers, using ionic liquids or other ion-containing liquids as solvent. Chitin fibers produced thereby and articles containing such chitin fibers are also disclosed. The chitin fiber thus obtained has very high surface area and improved strength over currently commercially available chitin materials.

Membranes for redox flow battery applications.

PubMed

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-06-19

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

'Soft' amplifier circuits based on field-effect ionic transistors.

PubMed

Boon, Niels; Olvera de la Cruz, Monica

2015-06-28

Soft materials can be used as the building blocks for electronic devices with extraordinary properties. We introduce a theoretical model for a field-effect transistor in which ions are the gated species instead of electrons. Our model incorporates readily-available soft materials, such as conductive porous membranes and polymer-electrolytes to represent a device that regulates ion currents and can be integrated as a component in larger circuits. By means of Nernst-Planck numerical simulations as well as an analytical description of the steady-state current we find that the responses of the system to various input voltages can be categorized into ohmic, sub-threshold, and active modes. This is fully analogous to what is known for the electronic field-effect transistor (FET). Pivotal FET properties such as the threshold voltage and the transconductance crucially depend on the half-cell redox potentials of the source and drain electrodes as well as on the polyelectrolyte charge density and the gate material work function. We confirm the analogy with the electronic FETs through numerical simulations of elementary amplifier circuits in which we successfully substitute the electronic transistor by an ionic transistor.