Volatilization and Thermal Decomposition Mechanisms of Room-Temperature Ionic Liquids (PRE-PRINT)

DTIC Science & Technology

2017-03-07

Huang, X. J. & Chen, L. Q. “Novel room temperature molten salt electrolyte based on LiTFSI and acetamide for lithium batteries .” Electrochemistry...organic compounds (VOCs) used as industrial solvents with involatile liquids. RTILs also show promise for applications in fuel cells, batteries , solar...indicated that volatilization of these species occurs as a single ion pair. Recent ALS studies on the photoionization of other 1- alkyl-3

Surface-active ionic liquids for palladium-catalysed cross coupling in water: effect of ionic liquid concentration on the catalytically active species† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ra07757b

PubMed Central

Taskin, Meltem; Cognigni, Alice; Zirbs, Ronald; Reimhult, Erik

2017-01-01

We report the design and synthesis of surface-active ionic liquids for application in palladium-catalyzed cross coupling reactions. A series of dodecylimidazolium-based ionic liquids were applied as additives in the Heck reaction of ethyl acrylate and iodobenzene, and high yields of >90% could be obtained in water without the addition of further ligands. Our results indicate that the ionic liquid concentration in water is the key factor affecting the formation of the catalytically active species and hence the yield. Moreover, imidazolium-based ionic liquids that are able to form a carbene species differ significantly from conventional cationic surfactants, as a concentration dependent formation of the N-heterocyclic carbene complex was observed. PMID:29308189

Molecular and ionic mimicry and the transport of toxic metals

PubMed Central

Bridges, Christy C.; Zalups, Rudolfs K.

2008-01-01

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport of selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues. PMID:15845419

Molecular and ionic mimicry and the transport of toxic metals

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

Bridges, Christy C.; Zalups, Rudolfs K.

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport ofmore » selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues.« less

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.

Superbase-derived protic ionic liquids

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

Dai, Sheng; Luo, Huimin; Baker, Gary A.

2013-09-03

Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

Ionic liquid-functionalized mesoporous sorbents and their use in the capture of polluting gases

DOEpatents

Lee, Jong Suk; Koros, William J.; Bhuwania, Nitesh; Hillesheim, Patrick C.; Dai, Sheng

2016-01-12

A composite structure for capturing a gaseous electrophilic species, the composite structure comprising mesoporous refractory sorbent particles on which an ionic liquid is covalently attached, wherein said ionic liquid includes an accessible functional group that is capable of binding to said gaseous electrophilic species. In particular embodiments, the mesoporous sorbent particles are contained within refractory hollow fibers. Also described is a method for capturing a gaseous electrophilic species by use of the above-described composite structure, wherein the gaseous electrophilic species is contacted with the composite structure. In particular embodiments thereof, cooling water is passed through the refractory hollow fibers containing the IL-functionalized sorbent particles in order to facilitate capture of the gaseous electrophilic species, and then steam is passed through the refractory hollow fibers to facilitate release of the gaseous electrophilic species such that the composite structure can be re-used to capture additional gas.

Transition of Femtosecond-Filament-Solid Interactions from Single to Multiple Filament Regime

DOE PAGES

Skrodzki, P. J.; Burger, M.; Jovanovic, I.

2017-10-06

High-peak-power fs-laser filaments offer unique characteristics attractive to remote sensing via techniques such as remote laser-induced breakdown spectroscopy (R-LIBS). The dynamics of several ablation mechanisms following the interaction between a filament and a solid determines the emission strength and reproducibility of target plasma, which is of relevance for R-LIBS applications. Here, we investigate the space- and time-resolved dynamics of ionic and atomic emission from copper as well as the surrounding atmosphere in order to understand limitations of fs-filament-ablation for standoff energy delivery. Furthermore, we probe the shock front produced from filament-target interaction using time-resolved shadowgraphy and infer laser-material coupling efficienciesmore » for both single and multiple filament regimes through analysis of shock expansion with the Sedov model for point detonation. The results provide insight into plasma structure for the range of peak powers up to 30 times the critical power for filamentation P cr. Despite the stochastic nucleation of multiple filaments at peak-powers greater than 16 P cr, emission of ionic and neutral species increases with pump beam intensity, and short-lived nitrogen emission originating from the ambient is consistently observed. Ultimately, results suggest favorable scaling of emission intensity from target species on the laser pump energy, furthering the prospects for use of filament-solid interactions for remote sensing.« less

Transition of Femtosecond-Filament-Solid Interactions from Single to Multiple Filament Regime

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

Skrodzki, P. J.; Burger, M.; Jovanovic, I.

High-peak-power fs-laser filaments offer unique characteristics attractive to remote sensing via techniques such as remote laser-induced breakdown spectroscopy (R-LIBS). The dynamics of several ablation mechanisms following the interaction between a filament and a solid determines the emission strength and reproducibility of target plasma, which is of relevance for R-LIBS applications. Here, we investigate the space- and time-resolved dynamics of ionic and atomic emission from copper as well as the surrounding atmosphere in order to understand limitations of fs-filament-ablation for standoff energy delivery. Furthermore, we probe the shock front produced from filament-target interaction using time-resolved shadowgraphy and infer laser-material coupling efficienciesmore » for both single and multiple filament regimes through analysis of shock expansion with the Sedov model for point detonation. The results provide insight into plasma structure for the range of peak powers up to 30 times the critical power for filamentation P cr. Despite the stochastic nucleation of multiple filaments at peak-powers greater than 16 P cr, emission of ionic and neutral species increases with pump beam intensity, and short-lived nitrogen emission originating from the ambient is consistently observed. Ultimately, results suggest favorable scaling of emission intensity from target species on the laser pump energy, furthering the prospects for use of filament-solid interactions for remote sensing.« less

Phosphonium-based ionic liquids and their use in the capture of polluting gases

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

Dai, Sheng; Wang, Congmin; Luo, Huimin

2017-06-06

An ionic liquid composition having the following chemical structural formula: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from hydrocarbon groups containing at least 1 and up to 20 carbon atoms, and X.sup.- is a cyclic anion that possesses a negatively-charged group reactive with a gaseous electrophilic species, particularly carbon dioxide or sulfur dioxide. Methods for capturing a gaseous electrophilic species, such as CO.sub.2 or SO.sub.2, by contacting the gaseous electrophilic species with an ionic liquid according to Formula (1) are also described.

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.

Synthesis, morphology and dynamics of polyureas and their lithium ionomers

NASA Astrophysics Data System (ADS)

Chuayprakong, Sunanta

Electrolytes currently used in commercial lithium ion batteries have led to leakage and safety issues. Solvent-free solid polymer electrolytes (SPEs) offering high energy density are promising materials for lithium battery applications. SPEs require high modulus to separate the electrodes and suppress lithium dendrite growth. Microphase separation of the hard segments in amorphous polyureas (PUs) yields materials with higher moduli than typical low glass transition temperature (Tg) polymers. In this dissertation, several families of solution polymerized polyether-based PU ionomers were synthesized and their thermal, morphology and dynamic properties characterized as a function of chemical composition. In the initial phase of this investigation, polyethylene oxide (PEO) diamines (with molecular weights = 200, 600, 1050, 2000, 3000 and 6000 g/mol) were polymerized with 4,4' methylene diphenyl diisocyanate (MDI). PUs with 200 and 600 g/mol PEO soft segments are amorphous and single phase. The amorphous PU having 1050 g/mol PEO segments exhibits a small degree of phase separation, as demonstrated by X-ray scattering. PUs with 2000, 3000 and 6000 g/mol PEO soft segments are semicrystalline and their melting points and degrees of crystallinity are lower than those of the precursor PEO diamines due to their attachment to rigid hard segments. Even though polypropylene oxide (PPO) does not dissolve cations as efficiently as PEO, PPO is not crystallizable and was chosen to create a second family of amorphous PUs. PPO-containing diamines ((Jeff400 (MW = 400 g/mol) and Jeff2000 (MW = 2000 g/mol)) and MDI were chosen as the neutral soft segment and the hard segment, respectively. 2,5-diaminobenzene sulfonate was successfully synthesized and used for preparing ionomers. The amount of ionic species in these ionomers was varied and quantified using 1H-NMR. Single Tgs were observed and they increased with increasing ionic content. No X-ray scattering peaks corresponding to microphase separation of hard and soft segments were detected, nor were ordered hydrogen bonded carbonyl bands in FTIR spectra, demonstrating that the Jeff400 PUs are single phase. Using dielectric relaxation spectroscopy (DRS), segmental relaxation temperatures also increase with increasing ionic species content.. Increasing the number of ionic groups increases the hard segment content, which results in higher DSC Tgs and slower fmaxs for the segmental relaxation processes. For the non-ionic and all of the ionic Jeff2000 PU samples that contain some nonionic soft segments, low temperature Tgs were observed that arise from microphase separated soft phases. X-ray scattering peaks related to microphase separation and ordered hydrogen bonded carbonyl bands were observed, reinforcing the conclusion of hard/soft segment segregation. The DRS segmental relaxation is associated with soft phase relaxation, with some of the ion dipoles participating in this process for the ionic samples. The ionomers could not be dialyzed due to water insolubility, but were purified by multiple precipitation in deionize water. Nevertheless, the findings suggest that the observed conductivity primarily arises from ionic impurities. A third family of PU ionomers was synthesized using an amorphous polypropylene oxide-b- polyethylene oxide-b-polypropylene oxide diamine (ED900, MW = 900 g/mol, 68% EO) and 2,5-diaminobenzene sulfonate. Hexamethylene diisocyanate was utilized as the hard segment as its high packing efficiency is known to facilitate microphase separation. The non-ionic ED900 PU and its ionomers with various ion contents were successfully synthesized. Low Tgs due to segregation of soft segments, X-ray scattering peaks related to microphase separation between segments, and ordered hydrogen bonded carbonyl bands were detected. Tapping mode atomic force microscopy was also used to explore the morphology of these microphase separated materials. DRS segmental relaxations are associated with soft phase. These materials were extensively dialyzed and their low conductivities suggest that the lithium ions are primarily trapped in hard domains.

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

Xiong, Haifeng; Lin, Sen; Goetze, Joris

CeO2 supports are unique in their ability to trap ionic Pt, providing exceptional stability for isolated single atoms of Pt. Here, we explore the reactivity and stability of single atom Pt species for the industrially important reaction of light alkane dehydrogenation. The single atom Pt/CeO2 catalysts are stable during propane dehydrogenation, but we observe no selectivity towards propene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when Sn is added to ceria, the single atom Pt catalyst undergoes an activation phase where it transforms into Pt-Sn clusters under reaction conditions. Formation ofmore » small Pt-Sn clusters allows the catalyst to achieve high selectivity towards propene, due to facile desorption of the product. The CeO2-supported Pt-Sn clusters are very stable, even during extended reaction at 680 °C. By adding water vapor to the feed, coke formation can almost completely be suppressed. Furthermore, the Pt-Sn clusters can be readily transformed back to the atomically dispersed species on ceria via oxidation, making Pt-Sn/CeO2 a fully regenerable catalyst.« less

Tuning transport selectivity of ionic species by phosphoric acid gradient in positively charged nanochannel membranes.

PubMed

Yang, Meng; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Fan, Xin; Liu, Wei; Liu, Xizhen; Liu, Jianbo; Huang, Jin

2015-02-03

The transport of ionic species through a nanochannel plays important roles in fundamental research and practical applications of the nanofluidic device. Here, we demonstrated that ionic transport selectivity of a positively charged nanochannel membrane can be tuned under a phosphoric acid gradient. When phosphoric acid solution and analyte solution were connected by the positively charged nanochannel membrane, the faster-moving analyte through the positively charged nanochannel membrane was the positively charged dye (methylviologen, MV(2+)) instead of the negatively charged dye (1,5-naphthalene disulfonate, NDS(2-)). In other words, a reversed ion selectivity of the nanochannel membranes can be found. It can be explained as a result of the combination of diffusion, induced electroosmosis, and induced electrophoresis. In addition, the influencing factors of transport selectivity, including concentration of phosphoric acid, penetration time, and volume of feed solution, were also investigated. The results showed that the transport selectivity can further be tuned by adjusting these factors. As a method of tuning ionic transport selectivity by establishing phosphoric acid gradient, it will be conducive to improving the separation of ionic species.

Synergistic Impacts of Electrolyte Adsorption on the Thermoelectric Properties of Single-Walled Carbon Nanotubes.

PubMed

Nakano, Motohiro; Nakashima, Takuya; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki

2017-08-01

Single-walled carbon nanotubes are promising candidates for light-weight and flexible energy materials. Recently, the thermoelectric properties of single-walled carbon nanotubes have been dramatically improved by ionic liquid addition; however, controlling factors remain unsolved. Here the thermoelectric properties of single-walled carbon nanotubes enhanced by electrolytes are investigated. Complementary characterization with absorption, Raman, and X-ray photoelectron spectroscopy reveals that shallow hole doping plays a partial role in the enhanced electrical conductivity. The molecular factors controlling the thermoelectric properties of carbon nanotubes are systematically investigated in terms of the ionic functionalities of ionic liquids. It is revealed that appropriate ionic liquids show a synergistic enhancement in conductivity and the Seebeck coefficient. The discovery of significantly precise doping enables the generation of thermoelectric power factor exceeding 460 µW m - 1 K -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

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

Praveen, D.; Damle, Ramakrishna

2016-05-23

Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in themore » past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.« less

Self-doped microphase separated block copolymer electrolyte

DOEpatents

Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

2002-01-01

A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

Ionic association of lithium salts in propylene carbonate/ 1,2-dimethoxyethane mixed systems for lithium batteries

NASA Astrophysics Data System (ADS)

Ishikawa, Masashi; Wen, Shi-Qui; Matsuda, Yoshiharu

1993-06-01

The ionic association constants of lithium perchlorate, lithium trifluoremethylsulfate, lithium hexafluorophosphate, and lithium tetrafluoroborate have been determined experimentally (by Shedlovsky's method) in various mixtures of propylene carbonate and 1,2-dimethoxyethane as typical electrolyte systems for rechargeable lithium batteries. The association constants vary extensively for different mixing ratios of propylene to 1,2-dimethoxyethane and for different species of salts. These values are compared with the theoretical values as predicted by the Fuoss and Bjerrum equations. On the basis of this comparison and some physical properties of the solution, the variation in the ionic association constants may be ascribed to the charge of ionic association species, i.e., a contact ion-pair and a solvent-separated ion-pair.

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

Solvation of apolar compounds in protic ionic liquids: the non-synergistic effect of electrostatic interactions and hydrogen bonds.

PubMed

Sedov, I A; Magsumov, T I; Salikov, T M; Solomonov, B N

2017-09-27

The solvation properties of protic ionic liquids such as alkylammonium salts are still virtually uncharacterized. Both electrostatic interactions between charged particles and hydrogen bond networks in a solvent are known to hinder the solubility of apolar species. Protic ionic liquids can be a priori expected to dissolve hydrocarbons worse than aprotic ionic liquids which do not form hydrogen bonds between the ions. We measured the limiting activity coefficients of several alkanes and alkylbenzenes in propylammonium and butylammonium nitrates at 298 K. Surprisingly, we observed the tendency of higher solubility than for the same compounds in aprotic ionic liquids with a similar molar volume. The calculations of the excess Gibbs free energies using test particle insertions into the snapshots of molecular dynamics trajectories reproduced lower values in protic rather than in aprotic ionic liquids for both methane molecules and hard sphere solutes. This can be explained by the favorable solvation of apolar species in the apolar domain of nanostructured PILs. For the first time, we point out at the essential difference between the solvation properties of two types of ionic liquids and prove that it arises from the cavity formation term.

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

Solvation structures of water in trihexyltetradecylphosphonium-orthoborate ionic liquids

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

Wang, Yong-Lei, E-mail: wangyonl@gmail.com; System and Component Design, Department of Machine Design, KTH Royal Institute of Technology, SE-100 44 Stockholm; Sarman, Sten

2016-08-14

Atomistic molecular dynamics simulations have been performed to investigate effective interactions of isolated water molecules dispersed in trihexyltetradecylphosphonium-orthoborate ionic liquids (ILs). The intrinsic free energy changes in solvating one water molecule from gas phase into bulk IL matrices were estimated as a function of temperature, and thereafter, the calculations of potential of mean force between two dispersed water molecules within different IL matrices were performed using umbrella sampling simulations. The systematic analyses of local ionic microstructures, orientational preferences, probability and spatial distributions of dispersed water molecules around neighboring ionic species indicate their preferential coordinations to central polar segments in orthoboratemore » anions. The effective interactions between two dispersed water molecules are partially or totally screened as their separation distance increases due to interference of ionic species in between. These computational results connect microscopic anionic structures with macroscopically and experimentally observed difficulty in completely removing water from synthesized IL samples and suggest that the introduction of hydrophobic groups to central polar segments and the formation of conjugated ionic structures in orthoborate anions can effectively reduce residual water content in the corresponding IL samples.« less

Systematic Approach for Calculating the Concentrations of Chemical Species in Multiequilibrium Problems: Inclusion of the Ionic Strength Effects

ERIC Educational Resources Information Center

Baeza-Baeza, Juan J.; Garcia-Alvarez-Coque, M. Celia

2012-01-01

A general systematic approach including ionic strength effects is proposed for the numerical calculation of concentrations of chemical species in multiequilibrium problems. This approach extends the versatility of the approach presented in a previous article and is applied using the Solver option of the Excel spreadsheet to solve real problems…

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

Polarographic determination of lead hydroxide formation constants at low ionic strength

USGS Publications Warehouse

Lind, Carol J.

1978-01-01

Values of formation constants for lead hydroxide at 25 ??C were calculated from normal pulse polarographic measurements of 10-6 M lead in 0.01 M sodium perchlorate. The low concentrations simulate those found in many freshwaters, permitting direct application of the values when considering distributions of lead species. The precise evaluation of species distribution in waters at other ionic strengths requires activity coefficient corrections. As opposed to much of the previously published work done at high ionic strength, the values reported here were obtained at low ionic strength, permitting use of smaller and better defined activity coefficient corrections. These values were further confirmed by differential-pulse polarography and differential-pulse anodic stripping voltammetry data. The logs of the values for ??1??? ??2???, and ??3??? were calculated to be 6.59, 10.80, and 13.63, respectively. When corrected to zero ionic strength these values were calculated to be 6.77, 11.07, and 13.89, respectively.

Challenges in Determining Intrinsic Viscosity Under Low Ionic Strength Solution Conditions.

PubMed

Pindrus, Mariya A; Shire, Steven J; Yadav, Sandeep; Kalonia, Devendra S

2017-04-01

To determine the intrinsic viscosity of several monoclonal antibodies (mAbs) under varying pH and ionic strength solution conditions. An online viscosity detector attached to HPLC (Viscotek®) was used to determine the intrinsic viscosity of mAbs. The Ross and Minton equation was used for viscosity prediction at high protein concentrations. Bulk viscosity was determined by a Cambridge viscometer. At 15 mM ionic strength, intrinsic viscosity of the mAbs determined by the single-point approach varied from 5.6 to 6.4 mL/g with changes in pH. High ionic strength did not significantly alter intrinsic viscosity, while a significant increase (up to 24.0 mL/g) was observed near zero mM. No difference in bulk viscosity of mAb3 was observed around pH 6 as a function of ionic strength. Data analysis revealed that near zero mM ionic strength limitations of the single-point technique result in erroneously high intrinsic viscosity. Intrinsic viscosity is a valuable tool that can be used to model baseline viscosity at higher protein concentrations. However, it is not predictive of solution non-ideality at higher protein concentrations. Furthermore, breakdown of numerous assumptions limits the applicability of experimental techniques near zero mM ionic strength conditions. For molecules and conditions studied, the single-point approach produced reliable intrinsic viscosity results at 15 mM. However, this approach must be used with caution near zero mM ionic strength. Data analysis can be used to reveal whether determined intrinsic viscosity is reliable or erroneously high.

Nanostructure and Dynamics of Ionic and Non-Ionic PEO-Containing Polyureas

NASA Astrophysics Data System (ADS)

Chuayprakong, Sunanta; Runt, James

2013-03-01

A series of polyethylene oxide (PEO) - based diamines with molecular weights ranging from 250 - 6000 g/mol were polymerized in solution with 4,4'-methylene diphenyl diisocyanate (MDI). In addition, PEO soft segment diamines where modified to incorporate ionomeric species and also polymerized with MDI. The role of PEO soft segment molecular weight and the presence of ionic species on nanoscale segregation and cation conductivity were explored. The former was investigated using small-angle X-ray scattering and atomic force microscopy. Dielectric relaxation spectroscopy was used to investigate polymer and ion dynamics. Local environment and hydrogen bonding were identified by using FTIR spectroscopy.

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.

Membrane contactor assisted extraction/reaction process employing ionic liquids

DOEpatents

Lin, Yupo J [Naperville, IL; Snyder, Seth W [Lincolnwood, IL

2012-02-07

The present invention relates to a functionalized membrane contactor extraction/reaction system and method for extracting target species from multi-phase solutions utilizing ionic liquids. One preferred embodiment of the invented method and system relates to an extraction/reaction system wherein the ionic liquid extraction solutions act as both extraction solutions and reaction mediums, and allow simultaneous separation/reactions not possible with prior art technology.

Rotational dynamics of imidazolium-based ionic liquids: do the nature of the anion and the length of the alkyl chain influence the dynamics?

PubMed

Prabhu, Sugosh R; Dutt, G B

2014-11-20

The rotational dynamics of 1-alkyl-3-methylimidazolium-based ionic liquids has been investigated by monitoring their inherent fluorescence with the intent to unravel the characteristics of the emitting species. For this purpose, temperature-dependent fluorescence anisotropies of 1-alkyl-3-methylimidazolium (alkyl = ethyl and hexyl) ionic liquids with anions such as tris(pentafluoroethyl)trifluorophosphate ([FAP]), bis(trifluoromethylsulfonyl)imide ([Tf2N]), tetrafluoroborate ([BF4]), and hexafluorophosphate ([PF6]) have been measured. It has been observed that the reorientation times (τr) of the ionic liquids with an ethyl chain scale linearly with viscosity and were found to be independent of the nature of the anion. The experimentally measured τr values are a factor of 3 longer than the ones calculated for 1-ethyl-3-methylimidazolium cation using the Stokes-Einstein-Debye (SED) hydrodynamic theory with stick boundary condition, which suggests that the emitting species is not the imidazolium moiety but some kind of associated species. The reorientation times of ionic liquids with a hexyl chain, in contrast, follow the trend τr([FAP]) > τr([Tf2N]) = τr([BF4]) > τr([PF6]) at a given viscosity (η) and temperature (T). The ability of the ionic liquids with longer alkyl chains to form the organized structure appears to be responsible for the observed behavior considering the fact that significant deviations from linearity have been noticed in the τr versus η/T plots for strongly associating anions [BF4] and [PF6], especially at ambient temperatures.

Competitive Adsorption and Ordered Packing of Counterions near Highly Charged Surfaces: From Mean-Field Theory to Monte Carlo Simulations

PubMed Central

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2013-01-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson’s equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both of the mean-field theory and MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling. PMID:22680474

Competitive adsorption and ordered packing of counterions near highly charged surfaces: From mean-field theory to Monte Carlo simulations.

PubMed

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2012-04-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect-included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson's equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both the mean-field theory and the MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling.

Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

DTIC Science & Technology

2012-06-01

This method has been used previously with both PEM and AEM fuel cells and demonstrated its ability to accurately predict ionic conductivity [2,9,24...water. In an AMFC, the mobile species is a hydroxide ion (OH - ) and in a PEM fuel cell , the proton is solvated with a water molecule forming...membrane synthesis techniques have produced polymer electrolyte membranes that are capable of transporting anions in alkaline membrane fuel cells

New insight into the environmental impact of two imidazolium ionic liquids. Effects on seed germination and soil microbial activity.

PubMed

Salgado, J; Parajó, J J; Teijeira, T; Cruz, O; Proupín, J; Villanueva, M; Rodríguez-Añón, J A; Verdes, P V; Reyes, O

2017-10-01

The next generation of ionic liquids must be synthetized taking into account structures that guarantee the suitable properties for a defined application as well as ecological data. Thus, searching of the right methodologies to know, quickly and efficiently, the ecological effects of these compounds is a preliminary task. The effects of two imidazolium based ionic liquids with different anions, 1-butyl-3-methylimidazolium tetrafluoroborate, [C 4 C 1 Im][BF 4 ], and 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C 3 C 1 Im][NTf 2 ], on seedling emergence of six tree species and on the microbial behaviour of two soils were determined in this work. Results showed that the highest doses of both ionic liquids caused the total inhibition of germination for almost all the species studied and that the seeds are more sensitive to the presence of these compounds than soil microbial activity. Nevertheless, signals of stress and death are observed from the results of heat released by microorganisms after the addition of the highest doses of both ionic liquids. The novelty of this work resides in the enlargement of knowledge of toxicity of ILs on complex organisms such as arboreal species and microbial activity of soils studied for the first time through a microcalorimetric technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

Escherichia coli identification and strain discrimination using nanosecond laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Diedrich, Jonathan; Rehse, Steven J.; Palchaudhuri, Sunil

2007-04-01

Three strains of Escherichia coli, one strain of environmental mold, and one strain of Candida albicans yeast have been analyzed by laser-induced breakdown spectroscopy using nanosecond laser pulses. All microorganisms were analyzed while still alive and with no sample preparation. Nineteen atomic and ionic emission lines have been identified in the spectrum, which is dominated by calcium, magnesium, and sodium. A discriminant function analysis has been used to discriminate between the biotypes and E. coli strains. This analysis showed efficient discrimination between laser-induced breakdown spectroscopy spectra from different strains of a single bacteria species.

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

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.

Supramolecular Assembly of a Biomineralizing Antimicrobial Peptide in Coarse-Grained Monte Carlo Simulations (Postprint)

DTIC Science & Technology

2010-07-05

aqueous solutions at a wide pH range.7 Silica forms rapidly at room temperature in the absence of other ionic catalysts or cofactors (buffers, salts...and other ionic species) that are normally required with in vitro biosilica synthesis. The silaffins are uniquely functionalized; serine residues are...alkaline conditions mimic the properties of the poly- ionic modifications on native silaffins.13,14 The zwitterionic properties facilitate intermolecular

Electrochemistry of sulfur and polysulfides in ionic liquids.

PubMed

Manan, Ninie S A; Aldous, Leigh; Alias, Yatimah; Murray, Paul; Yellowlees, Lesley J; Lagunas, M Cristina; Hardacre, Christopher

2011-12-01

The electrochemistry of elemental sulfur (S(8)) and the polysulfides Na(2)S(4) and Na(2)S(6) has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S(8) in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S(8) in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S(6)(2-) and S(4)(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S(6)(2-) and S(4)(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S(3)(•-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents. © 2011 American Chemical Society

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.

Chemical surface deposition of ultra-thin semiconductors

DOEpatents

McCandless, Brian E.; Shafarman, William N.

2003-03-25

A chemical surface deposition process for forming an ultra-thin semiconducting film of Group IIB-VIA compounds onto a substrate. This process eliminates particulates formed by homogeneous reactions in bath, dramatically increases the utilization of Group IIB species, and results in the formation of a dense, adherent film for thin film solar cells. The process involves applying a pre-mixed liquid coating composition containing Group IIB and Group VIA ionic species onto a preheated substrate. Heat from the substrate causes a heterogeneous reaction between the Group IIB and VIA ionic species of the liquid coating composition, thus forming a solid reaction product film on the substrate surface.

Lipid extraction from microalgae using a single ionic liquid

DOEpatents

Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

2013-05-28

A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

Dressed ion theory of size-asymmetric electrolytes: effective ionic charges and the decay length of screened Coulomb potential and pair correlations.

PubMed

Forsberg, Björn; Ulander, Johan; Kjellander, Roland

2005-02-08

The effects of ionic size asymmetry on long-range electrostatic interactions in electrolyte solutions are investigated within the primitive model. Using the formalism of dressed ion theory we analyze correlation functions from Monte Carlo simulations and the hypernetted chain approximation for size asymmetric 1:1 electrolytes. We obtain decay lengths of the screened Coulomb potential, effective charges of ions, and effective permittivity of the solution. It is found that the variation of these quantities with the degree of size asymmetry depends in a quite intricate manner on the interplay between the electrostatic coupling and excluded volume effects. In most cases the magnitude of the effective charge of the small ion species is larger than that of the large species; the difference increases with increasing size asymmetry. The effective charges of both species are larger (in absolute value) than the bare ionic charge, except for high asymmetry where the effective charge of the large ions can become smaller than the bare charge.

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

The chemical identity of intervessel pit membranes in Acer challenges hydrogel control of xylem hydraulic conductivity

PubMed Central

Klepsch, Matthias M.; Schmitt, Marco; Paul Knox, J.; Jansen, Steven

2016-01-01

Ion-mediated enhancement of the hydraulic conductivity of xylem tissue (i.e. the ionic effect) has been reported for various angiosperm species. One explanation of the ionic effect is that it is caused by the swelling and shrinking of intervessel pit membranes due to the presence of pectins and/or other cell-wall matrix polymers such as heteroxylans or arabinogalactan–proteins (AGPs) that may contain acidic sugars. Here, we examined the ionic effect for six Acer species and their pit membrane chemistry using immunocytochemistry, including antibodies against glycoproteins. Moreover, anatomical features related to the bordered pit morphology and vessel dimensions were investigated using light and electron microscopy. The ionic effect varied from 18 % (± 9) to 32 % (± 13). Epitopes of homogalacturonan (LM18) and xylan (LM11) were not detected in intervessel pit membranes. Negative results were also obtained for glycoproteins (extensin: LM1, JIM20; AGP glycan: LM2), although AGP (JIM13)-related epitopes were detected in parenchyma cells. The mean vessel length was significantly correlated with the magnitude of the ionic effect, unlike other pit or vessel-related characteristics. Our results suggest that intervessel pit membranes of Acer are unlikely to contain pectic or other acidic polysaccharides. Therefore, alternative explanations should be tested to clarify the ionic effect. PMID:27354661

Mesoporous poly(ionic liquid) supported palladium(II) catalyst for oxidative coupling of benzene under atmospheric oxygen

NASA Astrophysics Data System (ADS)

Liu, Yangqing; Wang, Kai; Hou, Wei; Shan, Wanjian; Li, Jing; Zhou, Yu; Wang, Jun

2018-01-01

Multi-functional mesoporous poly(ionic liquid) (MPIL) containing pyridine-based ionic liquid (IL) moieties and adjacent double sbnd COOH groups was synthesized through the free radical copolymerization of IL monomer N-propane sulfonate-4-vinylpyridine, maleic anhydride and divinylbenzene. Palladium(II) species were anchored on this MPIL support, affording the first efficient heterogeneous catalyst for the oxidative coupling of benzene to biphenyl under atmospheric oxygen at low temperature. The biphenyl yield of 15.0% (selectivity: 98.5%, turnover number: 62) was even higher than the one over the homogeneous counterpart palladium acetate. The catalyst can be facilely separated and reused. The IL moiety in the polymeric framework endowed the formation of immobilized palladium(II) species with high electrophilicity, which responds to the high performance.

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.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Effects of chemically induced contraction of a coordination polyhedron on the dynamical magnetism of bis(phthalocyaninato)disprosium, a single-4f-ionic single-molecule magnet with a Kramers ground state.

PubMed

Ishikawa, Naoto; Mizuno, Yoshifumi; Takamatsu, Satoshi; Ishikawa, Tadahiko; Koshihara, Shin-ya

2008-11-17

Chemically induced longitudinal contraction of the square-antiprism coordination polyhedron of a peripherically substituted bis(phthalocyaninato)dysprosiumate(III), a dysprosium-based single-4f-ionic single-molecule magnet having a J z = +/- (13)/ 2 Kramers doublet ground state, resulted in drastic changes in dynamical magnetism including a doubling of the energy barrier, a 2-order-of-magnitude decrease of the spin reversal rate, a significant rise of the blocking temperature, and the first observation of the emergence of a large remanent magnetization.

Relaxation and transport properties of Li+ ion conducting biocompatible material for battery application

NASA Astrophysics Data System (ADS)

Hegde, Shreedatta; Ravindrachary, V.; Praveena, S. D.; Guruswamy, B.; Sagar, Rohan N.; Sanjeev, Ganesh

2018-04-01

Solid polymer electrolyte based on lithium chloride doped Poly (vinyl) alcohol composites are prepared by solution casting method. XRD results show that the crystallinity of the polymer interrupted upon LiCl doping and amorphous nature increases with dopant concentration. Impedance analysis revealed that conductivity of PVA increases with doping level and maximum ionic conductivity is observed to be 6.69 × 10-3 S/cm for 15 wt% LiCl doped PVA composite at 353K. Wagner's polarization technique has been followed to calculate ion transport number for high conducting electrolyte and transient study confirmed the presence of single charge species within the polymer electrolyte.

Minimal models of electric potential oscillations in non-excitable membranes.

PubMed

Perdomo, Guillermo; Hernández, Julio A

2010-01-01

Sustained oscillations in the membrane potential have been observed in a variety of cellular and subcellular systems, including several types of non-excitable cells and mitochondria. For the plasma membrane, these electrical oscillations have frequently been related to oscillations in intracellular calcium. For the inner mitochondrial membrane, in several cases the electrical oscillations have been attributed to modifications in calcium dynamics. As an alternative, some authors have suggested that the sustained oscillations in the mitochondrial membrane potential induced by some metabolic intermediates depends on the direct effect of internal protons on proton conductance. Most theoretical models developed to interpret oscillations in the membrane potential integrate several transport and biochemical processes. Here we evaluate whether three simple dynamic models may constitute plausible representations of electric oscillations in non-excitable membranes. The basic mechanism considered in the derivation of the models is based upon evidence obtained by Hattori et al. for mitochondria and assumes that an ionic species (i.e., the proton) is transported via passive and active transport systems between an external and an internal compartment and that the ion affects the kinetic properties of transport by feedback regulation. The membrane potential is incorporated via its effects on kinetic properties. The dynamic properties of two of the models enable us to conclude that they may represent alternatives enabling description of the generation of electrical oscillations in membranes that depend on the transport of a single ionic species.

Millimeter-wave irradiation heating for operation of doped CeO2 electrolyte-supported single solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Che Abdullah, Salmie Suhana Binti; Teranishi, Takashi; Hayashi, Hidetaka; Kishimoto, Akira

2018-01-01

High operation temperature of solid oxide fuel cell (SOFC) results in high cell and operation cost, time consuming and fast cell degradation. Developing high performance SOFC that operates at lower temperature is required. Here we demonstrate 24 GHz microwave as a rapid heating source to replace conventional heating method for SOFC operation using 20 mol% Sm doped CeO2 electrolyte-supported single cell. The tested cell shows improvement of 62% in maximum power density at 630 °C under microwave heating. This improvement governs by bulk conductivity of the electrolyte. Investigation of ionic transference number reveals that the value is unchanged under microwave irradiation, confirming the charge carrier is dominated by oxygen ion species. This work shows a potential new concept of high performance as well as cost and energy effective SOFC.

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.

An equation for the prediction of human skin permeability of neutral molecules, ions and ionic species.

PubMed

Zhang, Keda; Abraham, Michael H; Liu, Xiangli

2017-04-15

Experimental values of permeability coefficients, as log K p , of chemical compounds across human skin were collected by carefully screening the literature, and adjusted to 37°C for the effect of temperature. The values of log K p for partially ionized acids and bases were separated into those for their neutral and ionic species, forming a total data set of 247 compounds and species (including 35 ionic species). The obtained log K p values have been regressed against Abraham solute descriptors to yield a correlation equation with R 2 =0.866 and SD=0.432 log units. The equation can provide valid predictions for log K p of neutral molecules, ions and ionic species, with predictive R 2 =0.858 and predictive SD=0.445 log units calculated by the leave-one-out statistics. The predicted log K p values for Na + and Et 4 N + are in good agreement with the observed values. We calculated the values of log K p of ketoprofen as a function of the pH of the donor solution, and found that log K p markedly varies only when ketoprofen is largely ionized. This explains why models that neglect ionization of permeants still yield reasonable statistical results. The effect of skin thickness on log K p was investigated by inclusion of two indicator variables, one for intermediate thickness skin and one for full thickness skin, into the above equation. The newly obtained equations were found to be statistically very close to the above equation. Therefore, the thickness of human skin used makes little difference to the experimental values of log K p . Copyright © 2017 Elsevier B.V. All rights reserved.

Charge ordering in ionic fluids mediate repulsive surface interactions

NASA Astrophysics Data System (ADS)

Dasbiswas, Kinjal; Ludwig, Nicholas B.; Zhang, Hao; Talapin, Dmitri; Vaikuntanathan, Suri

Recent experiments on ionic fluids, such as surface force measurements in organic ionic liquids and the observation of colloidal stability in inorganic molten salts, suggest the presence of long-ranged repulsive forces. These cannot be explained within the classical Debye-Hückel theory for dilute electrolytes. We argue that such repulsive interactions can arise from long-range (several nm) charge density oscillations induced by a surface that preferentially binds one of the ionic species in an ionic fluid. We present a continuum theory that accounts for such charge layering based on a frustrated Ising model that incorporates both long-range Coulombic and short-range steric interactions. The mean-field analytic treatment qualitatively matches results from molecular simulations. A careful analysis of the ionic correlation functions arising from such charge ordering may also explain the long electrostatic screening lengths observed in various ionic fluids and their non-monotonic dependence on the electrolyte concentration. We acknowledge the University of Chicago for support.

Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes [Structural Relaxation and Dynamics of Ionic-Neutral Block Copolymer Surfactant Complexes

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

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.

Structure–property relationships of ionic block copolymer (BCP) surfactant complexes are critical toward the progress of favorable engineering design of efficient charge-transport materials. In this paper, molecular dynamics simulations are used to understand the dynamics of charged-neutral BCP and surfactant complexes. The dynamics are examined for two different systems: charged-neutral double-hydrophilic and hydrophobic–hydrophilic block copolymers with oppositely charged surfactant moieties. The dynamics of the surfactant head, tails, and charges are studied for five different BCP volume fractions. We observe that the dynamics of the different species solely depend on the balance between electrostatic and entropic interactions between the charged species andmore » the neutral monomers. The favorable hydrophobic–hydrophobic interactions and the unfavorable hydrophobic–hydrophilic interactions determine the mobilities of the monomers. The dynamical properties of the charge species influence complex formation. Structural relaxations exhibit length-scale dependent behavior, with slower relaxation at the radius of gyration length-scale and faster relaxation at the segmental length-scale, consistent with previous results. The dynamical analysis correlates ion-exchange kinetics to the self-assembly behavior of the complexes.« less

Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes [Structural Relaxation and Dynamics of Ionic-Neutral Block Copolymer Surfactant Complexes

DOE PAGES

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.; ...

2017-06-21

Structure–property relationships of ionic block copolymer (BCP) surfactant complexes are critical toward the progress of favorable engineering design of efficient charge-transport materials. In this paper, molecular dynamics simulations are used to understand the dynamics of charged-neutral BCP and surfactant complexes. The dynamics are examined for two different systems: charged-neutral double-hydrophilic and hydrophobic–hydrophilic block copolymers with oppositely charged surfactant moieties. The dynamics of the surfactant head, tails, and charges are studied for five different BCP volume fractions. We observe that the dynamics of the different species solely depend on the balance between electrostatic and entropic interactions between the charged species andmore » the neutral monomers. The favorable hydrophobic–hydrophobic interactions and the unfavorable hydrophobic–hydrophilic interactions determine the mobilities of the monomers. The dynamical properties of the charge species influence complex formation. Structural relaxations exhibit length-scale dependent behavior, with slower relaxation at the radius of gyration length-scale and faster relaxation at the segmental length-scale, consistent with previous results. The dynamical analysis correlates ion-exchange kinetics to the self-assembly behavior of the complexes.« less

The effect of sulfate on selenate bioaccumulation in two freshwater primary producers: A duckweed (Lemna minor) and a green alga (Pseudokirchneriella subcapitata).

PubMed

Lo, Bonnie P; Elphick, James R; Bailey, Howard C; Baker, Josh A; Kennedy, Christopher J

2015-12-01

Predicting selenium bioaccumulation is complicated because site-specific conditions, including the ionic composition of water, affect the bioconcentration of inorganic selenium into the food web. Selenium tissue concentrations were measured in Lemna minor and Pseudokirchneriella subcapitata following exposure to selenate and sulfate. Selenium accumulation differed between species, and sulfate reduced selenium uptake in both species, indicating that ionic constituents, in particular sulfate, are important in modifying selenium uptake by primary producers. © 2015 SETAC.

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

Integral equation model for warm and hot dense mixtures.

PubMed

Starrett, C E; Saumon, D; Daligault, J; Hamel, S

2014-09-01

In a previous work [C. E. Starrett and D. Saumon, Phys. Rev. E 87, 013104 (2013)] a model for the calculation of electronic and ionic structures of warm and hot dense matter was described and validated. In that model the electronic structure of one atom in a plasma is determined using a density-functional-theory-based average-atom (AA) model and the ionic structure is determined by coupling the AA model to integral equations governing the fluid structure. That model was for plasmas with one nuclear species only. Here we extend it to treat plasmas with many nuclear species, i.e., mixtures, and apply it to a carbon-hydrogen mixture relevant to inertial confinement fusion experiments. Comparison of the predicted electronic and ionic structures with orbital-free and Kohn-Sham molecular dynamics simulations reveals excellent agreement wherever chemical bonding is not significant.

Biological Activity of Ionic Liquids and Their Application in Pharmaceutics and Medicine.

PubMed

Egorova, Ksenia S; Gordeev, Evgeniy G; Ananikov, Valentine P

2017-05-24

Ionic liquids are remarkable chemical compounds, which find applications in many areas of modern science. Because of their highly tunable nature and exceptional properties, ionic liquids have become essential players in the fields of synthesis and catalysis, extraction, electrochemistry, analytics, biotechnology, etc. Apart from physical and chemical features of ionic liquids, their high biological activity has been attracting significant attention from biochemists, ecologists, and medical scientists. This Review is dedicated to biological activities of ionic liquids, with a special emphasis on their potential employment in pharmaceutics and medicine. The accumulated data on the biological activity of ionic liquids, including their antimicrobial and cytotoxic properties, are discussed in view of possible applications in drug synthesis and drug delivery systems. Dedicated attention is given to a novel active pharmaceutical ingredient-ionic liquid (API-IL) concept, which suggests using traditional drugs in the form of ionic liquid species. The main aim of this Review is to attract a broad audience of chemical, biological, and medical scientists to study advantages of ionic liquid pharmaceutics. Overall, the discussed data highlight the importance of the research direction defined as "Ioliomics", studies of ions in liquids in modern chemistry, biology, and medicine.

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.

Ionic conductivity of binary fluorides of potassium and rare earth elements

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

Sorokin, N. I., E-mail: nsorokin1@yandex.ru

2016-01-15

The ionic conductivity s of KYF{sub 4} and K{sub 2}RF{sub 5} single crystals (R = Gd, Ho, Er) and KNdF{sub 4} and K{sub 2}RF{sub 5} ceramic samples (R = Dy, Er) has been studied in the temperature range of 340–500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100–150 MPa) in the R{sub 2}O{sub 3}–KF–H{sub 2}O systems. The σ values of tetraf luorides are 3 × 10{sup –5} S/cm (KYF{sub 4} single crystal) and 3 × 10{sup –6}more » S/cm (KNdF{sub 4} ceramics) at 435°C. A K{sub 2}ErF{sub 5} single crystal with σ = 1.2 × 10{sup –4} S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K{sub 2}HoF{sub 5} single crystals, σ{sub ∥c}/σ{sub ⊥c} = 2.5, where σ{sub ∥c} and σ{sub ⊥c} are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.« less

First-principles investigations of ionic conduction in Li and Na borohydrides

NASA Astrophysics Data System (ADS)

Varley, Joel; Heo, Tae-Wook; Ray, Keith; Bonev, Stanimir; Wood, Brandon

Recent experimental studies have identified a family of alkali borohydride materials that exhibit superionic transition temperatures approaching room temperature and ionic conductivities exceeding 0.1 S/cm-1, making them highly promising solid electrolytes for next-generation batteries. Despite the rapid advances in improving the superionic conductivity in these materials, an understanding of the exact mechanisms driving the transport remains unknown. Here we use ab initio molecular dynamics calculations to address this issue by characterizing the diffusivity of the Li and Na species in a representative set of closoborane ionic conductors. We investigate both the Na and Li-containing borohydrides with icosahedral (B12H12) and double-capped square antiprism (B10H10) anion species and discuss the trends in ionic conductivity as a function of stoichiometry and the incorporation of various dopants. Our results support the borohydrides as a subset of a larger family of very promising solid electrolytes and identify strategies to improving the conductivity in these materials. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Varied incidence of immediate adverse reactions to low-osmolar non-ionic iodide radiocontrast media used in computed tomography.

PubMed

Kim, S R; Lee, J H; Park, K H; Park, H J; Park, J W

2017-01-01

Low-osmolar non-ionic radiocontrast media (RCMs) are commonly used throughout hospitals. However, the incidence of immediate adverse drug reactions (ADRs) to various low-osmolar non-ionic RCMs is not well studied. We compared the incidence of immediate ADRs among different low-osmolar non-ionic RCMs used in computed tomography (CT). Severance Hospital has collected data for adverse reactions occurring in-hospital using an internally developed system. Using this data, we reviewed 1969 immediate ADRs from 286 087 RCM-contrasted CT examinations of 142 099 patients and compared the immediate ADRs of iobitridol, iohexol, iopamidol, and iopromide. We analysed the incidence of immediate ADRs to different RCMs, as well as the effect of single or multiple CT examinations per day. Iopromide showed the highest incidence of immediate ADRs (1.03%) and was followed by iopamidol (0.67%), iohexol (0.64%), and iobitridol (0.34%). In cases of anaphylaxis, iopromide also showed the highest incidence (0.041%), followed by iopamidol (0.023%), iohexol (0.018%), and iobitridol (0.012%). Risk of immediate ADR due to multiple CT examinations (1.19%) was significantly higher than the risk due to a single CT examination (0.63%). Risk of anaphylaxis was also higher for multiple CT examinations (0.052%) than for a single CT examination (0.020%). The incidence of immediate ADRs varied according to the low-osmolar non-ionic RCM used. Iopromide-induced immediate ADRs were more frequent, while iobitridol was associated with fewer immediate ADRs than other RCMs. Multiple CT examinations per day resulted in a higher incidence of immediate ADRs and anaphylaxis than a single CT examination. Clinicians should consider these risk differences of immediate ADRs when prescribing contrasted CT examinations. © 2016 The Authors. Clinical & Experimental Allergy Published by John Wiley & Sons Ltd.

Secondary electrospray ionization of complex vapor mixtures. Theoretical and experimental approach.

PubMed

Vidal-de-Miguel, Guillermo; Herrero, Ana

2012-06-01

In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an electrospray plume become ionized after charge is transferred from the charging electrosprayed particles (the charging agent) to the vapor species. Currently available SESI models are valid for simplified systems having only one type of electrosprayed species, which ionizes only one single vapor species, and for the limit of low vapor concentration. More realistic models require considering other effects. Here we develop a theoretical model that accounts for the effects of high vapor concentration, saturation effects, interferences between different vapor species, and electrosprays producing different types of species from the liquid phase. In spite of the relatively high complexity of the problem, we find simple relations between the different ionic species concentrations that hold independently of the particular ion source configuration. Our model suggests that an ideal SESI system should use highly concentrated charging agents composed preferably of only one dominating species with low mobility. Experimental measurements with a MeOH-H(2)O-NH(3) electrospray and a mixture of fatty acids and lactic acid served to test the theory, which gives good qualitative results. These results also suggest that the SESI ionization mechanism is primarily based on ions rather than on charged droplets.

Ionic liquids. Combination of combustion calorimetry with high-level quantum chemical calculations for deriving vaporization enthalpies.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas; Schick, Christoph

2008-07-10

In this work, the molar enthalpies of formation of the ionic liquids [C2MIM][NO3] and [C4MIM][NO3] were measured by means of combustion calorimetry. The molar enthalpy of fusion of [C2MIM][NO3] was measured using differential scanning calorimetry. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. We have used a combination of traditional combustion calorimetry with modern high-level ab initio calculations in order to obtain the molar enthalpies of vaporization of a series of the ionic liquids under study.

Feasibility of a Supporting-Salt-Free Nonaqueous Redox Flow Battery Utilizing Ionic Active Materials.

PubMed

Milshtein, Jarrod D; Fisher, Sydney L; Breault, Tanya M; Thompson, Levi T; Brushett, Fikile R

2017-05-09

Nonaqueous redox flow batteries (NAqRFBs) are promising devices for grid-scale energy storage, but high projected prices could limit commercial prospects. One route to reduced prices is to minimize or eliminate the expensive supporting salts typically employed in NAqRFBs. Herein, the feasibility of a flow cell operating in the absence of supporting salt by utilizing ionic active species is demonstrated. These ionic species have high conductivities in acetonitrile (12-19 mS cm -1 ) and cycle at 20 mA cm -2 with energy efficiencies (>75 %) comparable to those of state-of-the-art NAqRFBs employing high concentrations of supporting salt. A chemistry-agnostic techno-economic analysis highlights the possible cost savings of minimizing salt content in a NAqRFB. This work offers the first demonstration of a NAqRFB operating without supporting salt. The associated design principles can guide the development of future active species and could make NAqRFBs competitive with their aqueous counterparts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry’s Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds

EPA Science Inventory

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry’s Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aq...

Ionic tracer movement through a Wyoming snowpack

Treesearch

Roger C. Bales; Richard A. Sommerfeld; David G. Kebler

1990-01-01

A meltwater ionic pulse with initial concentrations of 5-10 or more times the average was observed in lysimeters set at the base of a 2-m snowpack in an unpolluted, alpine watershed. Both background chemical species and added tracers exhibited the initial pulse. About 10 days after the onset of meltwater release, solute concentrations collected in the lysimeters...

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds

NASA Astrophysics Data System (ADS)

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; Xu, Wu; Helm, Monte L.; Burton, Sarah D.; Sorensen, Christina M.; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-09-01

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds.

PubMed

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M; Xu, Wu; Helm, Monte L; Burton, Sarah D; Sorensen, Christina M; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-09-16

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.

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

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Lastly, the electrochemicalmore » performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.« less

Ionic-Liquid-Infused Nanostructures as Repellent Surfaces.

PubMed

Galvan, Yaraset; Phillips, Katherine R; Haumann, Marco; Wasserscheid, Peter; Zarraga, Ramon; Vogel, Nicolas

2018-06-12

In order to prepare lubricant-infused repellent coatings on silica nanostructures using low vapor pressure ionic liquids as lubricants, we study the wetting behavior of a set of imidazolium-based ionic liquids with different alkyl side chains as a function of the applied surface functionalities. We take advantage of the structural color of inverse opals prepared from a colloidal coassembly technique to study the infiltration of ionic liquids into these nanoporous structures. We find that the more hydrophobic ionic liquids with butyl and hexyl side chains can completely infiltrate inverse opals functionalized with mixed self-assembled monolayers composed of imidazole groups and aliphatic hydrocarbon chains, which we introduce via silane chemistry. These molecular species reflect the chemical nature of the ionic liquid, thereby increasing the affinity between the liquid and solid surface. The mixed surface chemistry provides sufficiently small contact angles with the ionic liquid to infiltrate the nanopores while maximizing the contact angle with water. As a result, the mixed monolayers enable the design of a stable ionic liquid/solid interface that is able to repel water as a test liquid. Our results underline the importance of matching chemical affinities to predict and control the wetting behavior in complex, multiphase systems.

Ultrahigh-throughput exfoliation of graphite into pristine 'single-layer' graphene using microwaves and molecularly engineered ionic liquids.

PubMed

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards 'single-layer' graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml(-1), and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Ionic liquid-based single-drop microextraction/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene and xylene isomers in waters.

PubMed

Aguilera-Herrador, Eva; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

2008-08-01

The direct coupling between ionic liquid-based single-drop microextraction and gas chromatography/mass spectrometry is proposed for the rapid and simple determination of benzene, toluene, ethylbenzene and xylenes isomers (BTEX) in water samples. The extraction procedure exploits not only the high affinity of the selected ionic liquid (1-methyl-3-octyl-imidazolium hexaflourophosphate) to these aromatic compounds but also its special properties like viscosity, low vapour pressure and immiscibility with water. All the variables involved in the extraction process have been studied in depth. The developed method allows the determination of these single-ring compounds in water under the reference concentration level fixed by the international legislation. In this case, limits of detection were in the range 20 ng L(-1) (obtained for benzene) and 91 ng L(-1) (for o-xylene). The repeatability of the proposed method, expressed as RSD (n=5), varied between 3.0% (o-xylene) and 5.2% (toluene).

Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation

NASA Astrophysics Data System (ADS)

Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin

2016-02-01

Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.

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.

Insulated Conducting Cantilevered Nanotips and Two-Chamber Recording System for High Resolution Ion Sensing AFM

PubMed Central

Meckes, Brian; Arce, Fernando Teran; Connelly, Laura S.; Lal, Ratnesh

2014-01-01

Biological membranes contain ion channels, which are nanoscale pores allowing controlled ionic transport and mediating key biological functions underlying normal/abnormal living. Synthetic membranes with defined pores are being developed to control various processes, including filtration of pollutants, charge transport for energy storage, and separation of fluids and molecules. Although ionic transport (currents) can be measured with single channel resolution, imaging their structure and ionic currents simultaneously is difficult. Atomic force microscopy enables high resolution imaging of nanoscale structures and can be modified to measure ionic currents simultaneously. Moreover, the ionic currents can also be used to image structures. A simple method for fabricating conducting AFM cantilevers to image pore structures at high resolution is reported. Tungsten microwires with nanoscale tips are insulated except at the apex. This allows simultaneous imaging via cantilever deflections in normal AFM force feedback mode as well as measuring localized ionic currents. These novel probes measure ionic currents as small as picoampere while providing nanoscale spatial resolution surface topography and is suitable for measuring ionic currents and conductance of biological ion channels. PMID:24663394

The inorganic speciation of tin(II) in aqueous solution

NASA Astrophysics Data System (ADS)

Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2012-06-01

This paper reports new voltammetric measurements on the interactions between tin(II) and the most important natural inorganic ligands, OH-, Cl-, F-, CO32-, SO42- and PO43-. For a better understanding of tin(II) speciation, an analysis is also given of prior data on the same systems from the literature. The formation constants were determined at t = 25 °C in different ionic media and at different ionic strengths, specifically the following: Sn(OH)q (0.1 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), SnClr and Sn(OH)Cl (0.1 ⩽ I/mol L-1 ⩽ 2.3 in Na(NO3, Cl)), Sn(SO4)r (0.1 ⩽ I/mol L-1 ⩽ 1.6 in Na(NO3, SO4)), SnHqCO3 and SnHqPO4 (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), where the subscripts r and q represent the stoichiometric coefficients. Concerning the SnFr species, reliable literature values were considered (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaClO4). Fifteen voltammetric measurements were performed in synthetic seawater; the total seawater binding ability was evaluated by a model in which synthetic seawater is expressed as a single salt, BA. The formation of species between tin(II) and the anion of the marine salt (A) was also proposed, and the corresponding stability constants at different salinities (5 ⩽ S ⩽ 50) were reported. In addition, studies on the solubility of Sn(OH)2(s) were carried out using voltammetry and light scattering measurements. The "extra-stability" of the mixed species with respect to the parent species was evaluated, in particular for Sn(OH)Cl and the corresponding species involving the anion of the marine salt (A). The dependence of the formation constants on ionic strength was analysed using extended Debye-Hückel and Specific ion Interaction Theory (SIT) type equations. Tin(II) speciation was also evaluated in different natural fluid conditions, where, in all cases, carbonate complexation was predominant, hampering the formation of hydrolytic species throughout the investigated pH range. Moreover, some formation enthalpy changes were calculated for the Sn(OH)+, Sn(OH)2(aq), Sn(OH)2(s), Sn(OH)3-, Sn(OH)22+, Sn(OH)42+, Sn(OH)Cl, SnCl+, SnCl2 and SnCl3- species on the basis of the available literature stability constant values at different temperatures and using the empirical relationships reported in the literature. The ΔH values at t = 25 °C were positive in all cases except for the Sn(OH)2(s) and Sn(OH)3- species, indicating an increase in the stability constant values with increasing temperature. This work represents an advance in the knowledge, understanding and modelling of the inorganic speciation of tin(II) in natural fluids, particularly for solutions containing chloride, fluoride, sulphate, carbonate and phosphate anions.

Scalable Graphene-Based Membranes for Ionic Sieving with Ultrahigh Charge Selectivity.

PubMed

Hong, Seunghyun; Constans, Charlotte; Surmani Martins, Marcos Vinicius; Seow, Yong Chin; Guevara Carrió, Juan Alfredo; Garaj, Slaven

2017-02-08

Nanostructured graphene-oxide (GO) laminate membranes, exhibiting ultrahigh water flux, are excellent candidates for next generation nanofiltration and desalination membranes, provided the ionic rejection could be further increased without compromising the water flux. Using microscopic drift-diffusion experiments, we demonstrated the ultrahigh charge selectivity for GO membranes, with more than order of magnitude difference in the permeabilities of cationic and anionic species of equivalent hydration radii. Measuring diffusion of a wide range of ions of different size and charge, we were able to clearly disentangle different physical mechanisms contributing to the ionic sieving in GO membranes: electrostatic repulsion between ions and charged chemical groups; and the compression of the ionic hydration shell within the membrane's nanochannels, following the activated behavior. The charge-selectivity allows us to rationally design membranes with increased ionic rejection and opens up the field of ion exchange and electrodialysis to the GO membranes.

Electrode Reactions Coupled with Chemical Reactions of Oxygen, Water and Acetaldehyde in an Ionic Liquid: New Approaches for Sensing Volatile Organic Compounds.

PubMed

Chi, Xiaowei; Tang, Yongan; Zeng, Xiangqun

2016-10-20

Water and oxygen are ubiquitous present in ambient conditions. This work studies the unique oxygen, trace water and a volatile organic compound (VOC) acetaldehyde redox chemistry in a hydrophobic and aprotic ionic liquid (IL), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Bmpy] [NTf 2 ]) by cyclic voltammetry and potential step methods. One electron oxygen reduction leads to superoxide radical formation in the IL. Trace water in the IL acts as a protic species that reacts with the superoxide radical. Acetaldehyde is a stronger protic species than water for reacting with the superoxide radical. The presence of trace water in the IL was also demonstrated to facilitate the electro-oxidation of acetaldehyde, with similar mechanism to that in the aqueous solutions. A multiple-step coupling reaction mechanism between water, superoxide radical and acetaldehyde has been described. The unique characteristics of redox chemistry of acetaldehyde in [Bmpy][NTf 2 ] in the presence of oxygen and trace water can be controlled by electrochemical potentials. By controlling the electrode potential windows, several methods including cyclic voltammetry, potential step methods (single-potential, double-potential and triple-potential step methods) were established for the quantification of acetaldehyde. Instead of treating water and oxygen as frustrating interferents to ILs, we found that oxygen and trace water chemistry in [Bmpy][NTf 2 ] can be utilized to develop innovative electrochemical methods for electroanalysis of acetaldehyde.

Electrode Reactions Coupled with Chemical Reactions of Oxygen, Water and Acetaldehyde in an Ionic Liquid: New Approaches for Sensing Volatile Organic Compounds

PubMed Central

Chi, Xiaowei; Tang, Yongan; Zeng, Xiangqun

2017-01-01

Water and oxygen are ubiquitous present in ambient conditions. This work studies the unique oxygen, trace water and a volatile organic compound (VOC) acetaldehyde redox chemistry in a hydrophobic and aprotic ionic liquid (IL), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Bmpy] [NTf2]) by cyclic voltammetry and potential step methods. One electron oxygen reduction leads to superoxide radical formation in the IL. Trace water in the IL acts as a protic species that reacts with the superoxide radical. Acetaldehyde is a stronger protic species than water for reacting with the superoxide radical. The presence of trace water in the IL was also demonstrated to facilitate the electro-oxidation of acetaldehyde, with similar mechanism to that in the aqueous solutions. A multiple-step coupling reaction mechanism between water, superoxide radical and acetaldehyde has been described. The unique characteristics of redox chemistry of acetaldehyde in [Bmpy][NTf2] in the presence of oxygen and trace water can be controlled by electrochemical potentials. By controlling the electrode potential windows, several methods including cyclic voltammetry, potential step methods (single-potential, double-potential and triple-potential step methods) were established for the quantification of acetaldehyde. Instead of treating water and oxygen as frustrating interferents to ILs, we found that oxygen and trace water chemistry in [Bmpy][NTf2] can be utilized to develop innovative electrochemical methods for electroanalysis of acetaldehyde. PMID:29142331

Binary and ternary ionic compounds in the outer crust of accreted neutron stars

NASA Astrophysics Data System (ADS)

Chamel, N.

2017-12-01

The outer crust of an accreted neutron star is thought to contain a large distribution of different nuclear species resulting from the burying of ashes of X-ray bursts and superbursts. By analysing the stability of multicomponent Coulomb crystals against phase separation, it is found that various binary and ternary ionic compounds could be formed.

Size and Charge Dependence of Ion Transport in Human Nail Plate

PubMed Central

Baswan, Sudhir M.; Li, S. Kevin; LaCount, Terri D.; Kasting, Gerald B.

2016-01-01

The electrical properties of human nail plate are poorly characterized, yet are a key determinate of the potential to treat nail diseases such as onychomycosis using iontophoresis. In order to address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of −1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were three-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upwards of 5 Å (approximately MW ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. PMID:26886342

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.

Self-consistent field theory of polymer-ionic molecule complexation.

PubMed

Nakamura, Issei; Shi, An-Chang

2010-05-21

A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

Correlation between cation conduction and ionic morphology in a PEO-based single ion conductor

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2011-03-01

We use molecular dynamics simulation to study ion transport and backbone mobility of a PEO-based single ion conductor. Ion mobility depends on the chemical structure and the local environment of the ions, which consequently impact ionic conductivity. We characterize the aggregation state of the ions, and assess the role of ion complexes in ionomer dynamics. In addition to solvated cations and pairs, higher order ion clusters are found. Most of the ion clusters are in string-like structure and cross-link two or more different ionomer chains through ionic binding. Ionic crosslinks decrease mobility at the ionic co-monomer; hence the mobility of the adjacent PEO segment is influenced. Na ions show slow mobility when they are inside large clusters. The hopping timescale for Na varies from 20 ns to 200. A correlation is found between Na mobility and the number of hops from one coordination site to another. Besides ether oxygens, Na ions in the ionomer also use the anion and the edge of the cluster as hopping sites. The string-like structure of clusters provide less stable sites at the two ends thus ions are more mobile in those regions. We observed Grotthus like mechanism in our ionomer, in which the positive charge migrates within the string-like cluster without the cations actually moving.

Size mass distribution of water-soluble ionic species and gas conversion to sulfate and nitrate in particulate matter in southern Taiwan.

PubMed

Tsai, Jiun-Horng; Chang, Li-Peng; Chiang, Hung-Lung

2013-07-01

A Micro-Orifice Uniform Deposition Impactor (MOUDI) and a Nano-MOUDI were employed to determine the size-segregated mass distributions of ambient particulate matter (PM) and water-soluble ionic species for particulate constituents. In addition, gas precursors, including HCl, HONO, HNO3, SO2, and NH3 gases, were analyzed by an annular denuder system. PM size mass distribution, mass concentration, and ionic species concentration were measured during the day and at night during episode and non-episode periods in winter and summer. Average total suspended particle (TSP) concentrations during episode days in winter were as high as 153 ± 33 μg/m(3), and PM mass concentrations in summer were as low as one-third of that in winter. Generally, PM concentration at night was higher than that in the daytime in southern Taiwan during the sampling periods. In winter during the episode periods, the size-segregated mass distribution of PM mass concentration was mostly in the 0.32-3.2-μm range, and the PM concentration increased significantly in the range of 0.32-3.2 μm at night. Ammonium, nitrate, and sulfate were the dominant water-soluble ionic species in PM, contributing 34-48% of TSP mass. High concentrations of ammonia (12.9-49 μg/m(3)) and SO2 (2.6-27 μg/m(3)) were observed in the gas precursors. The conversion ratio was high in the PM size range of 0.18-3.2 μm both during the day and at night in winter, and the conversion ratio of episode days was 20% higher than that of non-episode days. The conversion factor was high for both nitrogen and sulfur species at nighttime, especially on episode days.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds

PubMed Central

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; Xu, Wu; Helm, Monte L.; Burton, Sarah D.; Sorensen, Christina M.; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-01-01

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability. PMID:26374254

Anion-tunable properties and electrochemical performance of functionalized ferrocene compounds

DOE PAGES

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; ...

2015-09-16

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Lastly, the electrochemicalmore » performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.« less

Liquid metal ion source and alloy for ion emission of multiple ionic species

DOEpatents

Clark, Jr., William M.; Utlaut, Mark W.; Wysocki, Joseph A.; Storms, Edmund K.; Szklarz, Eugene G.; Behrens, Robert G.; Swanson, Lynwood W.; Bell, Anthony E.

1987-06-02

A liquid metal ion source and alloy for the simultaneous ion evaporation of arsenic and boron, arsenic and phosphorus, or arsenic, boron and phosphorus. The ionic species to be evaporated are contained in palladium-arsenic-boron and palladium-arsenic-boron-phosphorus alloys. The ion source, including an emitter means such as a needle emitter and a source means such as U-shaped heater element, is preferably constructed of rhenium and tungsten, both of which are readily fabricated. The ion sources emit continuous beams of ions having sufficiently high currents of the desired species to be useful in ion implantation of semiconductor wafers for preparing integrated circuit devices. The sources are stable in operation, experience little corrosion during operation, and have long operating lifetimes.

Design of guanidinium ionic liquid based microwave-assisted extraction for the efficient extraction of Praeruptorin A from Radix peucedani.

PubMed

Ding, Xueqin; Li, Li; Wang, Yuzhi; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2014-12-01

A series of novel tetramethylguanidinium ionic liquids and hexaalkylguanidinium ionic liquids have been synthesized based on 1,1,3,3-tetramethylguanidine. The structures of the ionic liquids were confirmed by (1)H NMR spectroscopy and mass spectrometry. A green guanidinium ionic liquid based microwave-assisted extraction method has been developed with these guanidinium ionic liquids for the effective extraction of Praeruptorin A from Radix peucedani. After extraction, reversed-phase high-performance liquid chromatography with UV detection was employed for the analysis of Praeruptorin A. Several significant operating parameters were systematically optimized by single-factor and L9 (3(4)) orthogonal array experiments. The amount of Praeruptorin A extracted by [1,1,3,3-tetramethylguanidine]CH2CH(OH)COOH is the highest, reaching 11.05 ± 0.13 mg/g. Guanidinium ionic liquid based microwave-assisted extraction presents unique advantages in Praeruptorin A extraction compared with guanidinium ionic liquid based maceration extraction, guanidinium ionic liquid based heat reflux extraction and guanidinium ionic liquid based ultrasound-assisted extraction. The precision, stability, and repeatability of the process were investigated. The mechanisms of guanidinium ionic liquid based microwave-assisted extraction were researched by scanning electron microscopy and IR spectroscopy. All the results show that guanidinium ionic liquid based microwave-assisted extraction has a huge potential in the extraction of bioactive compounds from complex samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory Rotational Spectroscopy of the Interstellar Diatomic Hydride Ion SH+ (X 3Σ-)

NASA Astrophysics Data System (ADS)

Halfen, DeWayne; Ziurys, Lucy M.

2016-06-01

Diatomic hydride are among the most common molecular species in the interstellar medium (ISM). The low molecular mass and thus moments of inertia cause their rotational spectra to lie principally in the submillimeter and far-infrared regions. Diatomic hydrides, both neutral (MH) and ionic (MH+) forms, are also basic building blocks of interstellar chemistry. In ionic form, they may be the “hidden” carriers of refractory elements in dense gas. They are therefore extremely good targets for space-borne and airborne platforms such as Herschel, SOFIA, and SAFIR. However, in order to detect these species in the ISM, their rotational spectra must first be measured in the laboratory. To date, there is very little high resolution data available for many hydride species, in particular the ionic form. Using submillimeter/THz direct absorption methods in the Ziurys laboratory, spectra of the interstellar diatomic hydride SH+ (X 3Σ-) have been recorded. Recent work has concerned measurement of all three fine structure components of the fundamental rotational transition N = 1 ← 0 in the range 345 - 683 GHz. SH+ was generated from H2S and argon in an AC discharge. The data have been analyzed, and spectroscopic constants for this species have been refined. SH+ is found in Photon Dominated Regions (PDRs) and X-ray Dominated Regions (XDRs) and is thought to trace energetic processes in the ISM. These current measurements confirm recent observations of this species at submillimeter/THz wavelengths with ALMA and other ground-based telescopes.

Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

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

Seo, S; DeSilva, MA; Brennecke, JF

2014-12-25

Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange processmore » between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.« less

Enhancing thermoelectrochemical properties by tethering ferrocene to the anion or cation of ionic liquids: altered thermodynamics and solubility.

PubMed

Aldous, Leigh; Black, Jeffrey J; Elias, Maximo C; Gélinas, Bruno; Rochefort, Dominic

2017-09-13

Entropic changes inherent within a redox process typically result in significant temperature sensitivity. This can be utilised positively or can be a detrimental process. This study has investigated the thermoelectrochemical properties (temperature-dependant electrochemistry) of the ferrocenium|ferrocene redox couple in an ionic liquid, and in particular the effect of covalently tethering this redox couple to fixed positive or negative charges. As such, the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was employed to dissolve ferrocene, as well as cationic-tethered ferrocene (the 1-ethyl-3-(methylferrocenyl)imidazolium cation) and anionic-tethered ferrocene (the ferrocenylsulfonyl(trifluoromethylsulfonyl)imide anion). These systems were characterised in terms of their voltammetry (apparent formal potentials, diffusion coefficients and electron transfer rate constants) and thermoelectrochemistry (temperature coefficients of the cell potential or 'Seebeck coefficients', short circuit current densities and power density outputs). The oxidised cationic species behaved like a dicationic species and was thus 6-fold more effective at converting waste thermal energy to electrical power within a thermoelectrochemical cell than unmodified ferrocene. This was almost exclusively due to a significant boost in the Seebeck coefficient of this redox couple. Conversely, the oxidised anionic species was formally a zwitterion, but this zwitterionic species behaved thermodynamically like a neutral species. The inverted entropic change upon going from ferrocene to anion-tethered ferrocene allowed development of a largely temperature-insensitive reference potential based upon a mixture of acetylferrocene and ferricenyl(iii)sulfonyl(trifluoromethylsulfonyl)imide.

Fouling of nanofiltration, reverse osmosis, and ultrafiltration membranes by protein mixtures: the role of inter-foulant-species interaction.

PubMed

Wang, Yi-Ning; Tang, Chuyang Y

2011-08-01

Protein fouling of nanofiltration (NF), reverse osmosis (RO), and ultrafiltration (UF) membranes by bovine serum albumin (BSA), lysozyme (LYS), and their mixture was investigated under cross-flow conditions. The effect of solution chemistry, membrane properties, and permeate flux level was systematically studied. When the solution pH was within the isoelectric points (IEPs) of the two proteins (i.e., pH 4.7-10.4), the mixed protein system experienced more severe flux decline compared to the respective single protein systems, which may be attributed to the electrostatic attraction between the negatively charged BSA and positively charged LYS molecules. Unlike a typical single protein system, membrane fouling by BSA-LYS mixture was only weakly dependent on solution pH within this pH range, and increased ionic strength was found to enhance the membrane flux as a result of the suppressed BSA-LYS electrostatic attraction. Membrane fouling was likely controlled by foulant-fouled-membrane interaction under severe fouling conditions (elevated flux level and unfavorable solution chemistry that promotes fouling), whereas it was likely dominated by foulant-clean-membrane interaction under mild fouling conditions. Compared to nonporous NF and RO membranes, the porous UF membrane was more susceptible to dramatic flux decline due to the increased risk of membrane pore plugging. This study reveals that membrane fouling by mixed macromolecules may behave very differently from that by typical single foulant system, especially when the inter-foulant-species interaction dominates over the intra-species interaction in the mixed foulant system.

Sodiated Sugar Structures: Cryogenic Ion Vibrational Spectroscopy of Na^+(GLUCOSE) Adducts

NASA Astrophysics Data System (ADS)

Voss, Jonathan; Kregel, Steven J.; Fischer, Kaitlyn C.; Garand, Etienne

2017-06-01

The recent discovery that ionic liquids help facilitate the dissolution of cellulose has renewed interest in understanding how ionic species interact with carbohydrates. Here we present infrared spectra in the 2800 - 3800 \\wn range of gas-phase mass-selected Na^+(Glucose) adducts. These adducts are further probed with IR-dip spectroscopy to yield conformer specific spectra of at least seven unique species. The relative abundances of conformers show that gas-phase interconversion barriers are sufficiently high to preserve the solution-phase populations. Additionally, our results demonstrate that mM concentrations of NaCl do not strongly perturb the anomeric ratio of glucose in solution.

A novel strategy to evaluate the degradation of quantum dots: identification and quantification of CdTe quantum dots and corresponding ionic species by CZE-ICP-MS.

PubMed

Meng, Peijun; Xiong, Yamin; Wu, Yingting; Hu, Yue; Wang, Hui; Pang, Yuanfeng; Jiang, Shuqing; Han, Sihai; Huang, Peili

2018-05-09

In view of the significance and urgency of the speciation analysis of quantum dots (QDs) and their degradation products for clarifying their degradation rules and toxicity mechanisms, a method for the identification and quantification of CdTe QDs and corresponding ionic species in complex matrices was developed using capillary zone electrophoresis (CZE) coupled to inductively coupled plasma-mass spectrometry (ICP-MS). The quality assessment of commercial CdTe QDs and serum pharmacokinetics of synthesized CdTe QDs in rats were successfully undertaken using the developed CZE-ICP-MS method.

Evolution of ferroelectricity in tetrathiafulvalene-p-chloranil as a function of pressure and temperature

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

Dengl, Armin; Beyer, Rebecca; Peterseim, Tobias

2014-06-28

The neutral-to-ionic phase transition in the mixed-stack charge-transfer complex tetrathiafulvalene-p-chloranil (TTF-CA) has been studied by pressure-dependent infrared spectroscopy up to p = 11 kbar and down to low temperatures, T = 10 K. By tracking the C=O antisymmetric stretching mode of CA molecules, we accurately determine the ionicity of TTF-CA in the pressure-temperature phase diagram. At any point, the TTF-CA crystal bears only a single ionicity; there is no coexistence region or an exotic high-pressure phase. Our findings shed new light on the role of electron-phonon interaction in the neutral-ionic transition.

New laboratory approach to study Titan ionospheric chemistry

NASA Astrophysics Data System (ADS)

Thissen, R.; Dutuit, O.; Pernot, P.; Carrasco, N.; Lilensten, J.; Quirico, E.; Schmitt, B.

The exploration of Titan reveals a very complex chemistry occurring in the ionospheric region of the atmosphere. In order to interpret the observations performed by the Cassini spectrometers, we need to improve our description of the ion molecule chemistry involving nitrogen and hydrocarbons. Up to now, models are based on databases compiled over the years. These are quite complete to describe the major ions, but lack of accuracy for some of them, they totally neglect the questions of isomerization or chemical functionality in the description of ionic species and still miss a lot of inputs for ionic species heavier than 50 daltons. We propose to improve the databases by systematic measurements of ion molecule reaction rates, and further structural description, by means of a high resolution mass spectrometer, allowing for MS/MS structural analysis of the ionic species. A thorough evaluation of nowadays databases by means of uncertainty propagation will lead our choice of the most important reactions to be studied. This study shall also lead to educated choice for chemistry simplification, which is mandatory in order to include the chemistry in 3D or fluid models of the atmosphere. We plan as well to use extracts from tholins as molecular source for our analysis.

Probing the cellular damage in bacteria induced by GaN nanoparticles using confocal laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Sahoo, Prasana; Murthy, P. Sriyutha; Dhara, S.; Venugopalan, V. P.; Das, A.; Tyagi, A. K.

2013-08-01

Understanding the mechanism of nanoparticle (NP) induced toxicity in microbes is of potential importance to a variety of disciplines including disease diagnostics, biomedical implants, and environmental analysis. In this context, toxicity to bacterial cells and inhibition of biofilm formation by GaN NPs and their functional derivatives have been investigated against gram positive and gram negative bacterial species down to single cellular level. High levels of inhibition of biofilm formation (>80 %) was observed on treatments with GaN NPs at sub-micro molar concentrations. These results were substantiated with morphological features investigated with field emission scanning electron microscope, and the observed changes in vibrational modes of microbial cells using Raman spectroscopy. Raman spectra provided molecular interpretation of cell damage by registering signatures of molecular vibrations of individual living microbial cells and mapping the interplay of proteins at the cell membrane. As compared to the untreated cells, Raman spectra of NP-treated cells showed an increase in the intensities of characteristic protein bands, which confirmed membrane damage and subsequent release of cellular contents outside the cells. Raman spectral mapping at single cellular level can facilitate understanding of the mechanistic aspect of toxicity of GaN NPs. The effect may be correlated to passive diffusion causing mechanical damage to the membrane or ingress of Ga3+ (ionic radius 0.076 nm) which can potentially interfere with bacterial metabolism, as it resembles Fe2+ (ionic radius 0.077 nm), which is essential for energy metabolism.

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.

Sequential Vapor Infiltration Treatment Enhances the Ionic Current Rectification Performance of Composite Membranes Based on Mesoporous Silica Confined in Anodic Alumina.

PubMed

Liang, Yanyan; Liu, Zhengping

2016-12-20

Ionic current rectification of nanofluidic diode membranes has been studied widely in recent years because it is analogous to the functionality of biological ion channels in principle. We report a new method to fabricate ionic current rectification membranes based on mesoporous silica confined in anodic aluminum oxide (AAO) membranes. Two types of mesostructured silica nanocomposites, hexagonal structure and nanoparticle stacked structure, were used to asymmetrically fill nanochannels of AAO membranes by a vapor-phase synthesis (VPS) method with aspiration approach and were further modified via sequence vapor infiltration (SVI) treatment. The ionic current measurements indicated that SVI treatment can modulate the asymmetric ionic transport in prepared membranes, which exhibited clear ionic current rectification phenomenon under optimal conditions. The ionic current rectifying behavior is derived from the asymmetry of surface conformations, silica species components, and hydrophobic wettability, which are created by the asymmetrical filling type, silica depositions on the heterogeneous membranes, and the condensation of silanol groups. This article provides a considerable strategy to fabricate composite membranes with obvious ionic current rectification performance via the cooperation of the VPS method and SVI treatment and opens up the potential of mesoporous silica confined in AAO membranes to mimic fluid transport in biological processes.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

PubMed

Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

2012-04-21

Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. This journal is © the Owner Societies 2012

Ionic thermoelectric gating organic transistors

PubMed Central

Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

2017-01-01

Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins. PMID:28139738

Chromatin ionic atmosphere analyzed by a mesoscale electrostatic approach.

PubMed

Gan, Hin Hark; Schlick, Tamar

2010-10-20

Characterizing the ionic distribution around chromatin is important for understanding the electrostatic forces governing chromatin structure and function. Here we develop an electrostatic model to handle multivalent ions and compute the ionic distribution around a mesoscale chromatin model as a function of conformation, number of nucleosome cores, and ionic strength and species using Poisson-Boltzmann theory. This approach enables us to visualize and measure the complex patterns of counterion condensation around chromatin by examining ionic densities, free energies, shielding charges, and correlations of shielding charges around the nucleosome core and various oligonucleosome conformations. We show that: counterions, especially divalent cations, predominantly condense around the nucleosomal and linker DNA, unburied regions of histone tails, and exposed chromatin surfaces; ionic screening is sensitively influenced by local and global conformations, with a wide ranging net nucleosome core screening charge (56-100e); and screening charge correlations reveal conformational flexibility and interactions among chromatin subunits, especially between the histone tails and parental nucleosome cores. These results provide complementary and detailed views of ionic effects on chromatin structure for modest computational resources. The electrostatic model developed here is applicable to other coarse-grained macromolecular complexes. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

State-resolved Thermal/Hyperthermal Dynamics of Atmospheric Species

DTIC Science & Technology

2015-06-23

gas -room temperature ionic liquid (RTIL) interfaces. 2) Large scale trajectory simulations for theoretical analysis of gas - liquid scattering studies...areas: 1) Diode laser and LIF studies of hyperthermal CO2 and NO collisions at the gas -room temperature ionic liquid (RTIL) interfaces. 2) Large...scale trajectory simulations for theoretical analysis of gas - liquid scattering studies, 3) LIF data for state-resolved scattering of hyperthermal NO at

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Modeling solubility, acid-base properties and activity coefficients of amoxicillin, ampicillin and (+)6-aminopenicillanic acid, in NaCl(aq) at different ionic strengths and temperatures.

PubMed

Crea, Francesco; Cucinotta, Daniela; De Stefano, Concetta; Milea, Demetrio; Sammartano, Silvio; Vianelli, Giuseppina

2012-11-20

The total solubility of three penicillin derivatives was determined, in pure water and NaCl aqueous solutions at different salt concentrations (from ∼0.15 to 1.0 mol L(-1) for ampicillin and amoxicillin, and from ∼0.05 to 2.0 mol L(-1) for (+)6-aminopenicillanic acid), using the shake-flask method for generating the saturated solutions, followed by potentiometric analysis. The knowledge of the pH of solubilization and of the protonation constants determined in the same experimental conditions, allowed us to calculate, by means of the mass balance equations, the solubility of the neutral species at different ionic strength values, to model its dependence on the salt concentration and to determine the corresponding values at infinite dilution. The salting parameter and the activity coefficients of the neutral species were calculated by the Setschenow equation. The protonation constants of ampicillin and amoxicillin, determined at different temperatures (from T=288.15 to 318.15K), from potentiometric and spectrophotometric measurements, were used to calculate, by means of the Van't Hoff equation, the temperature coefficients at different ionic strength values and the corresponding protonation entropies. The protonation enthalpies of the (+)6-aminopenicillanic acid were determined by isoperibol calorimetric titrations at T=298.15K and up to I=2.0 mol L(-1). The dependence of the protonation constants on ionic strength was modeled by means of the Debye-Hückel and SIT (Specific ion Interaction Theory) approaches, and the specific interaction parameters of the ionic species were determined. The hydrolysis of the β-lactam ring was studied by spectrophotometric and H NMR investigations as a function of pH, ionic strength and time. Potentiometric measurements carried out on the hydrolyzed (+)6-aminopenicillanic acid allowed us to highlight that the opened and the closed β-lactam forms of the (+)6-aminopenicillanic acid have quite different acid-base properties. An analysis of literature solubility, protonation constants, enthalpies and activity coefficients is reported too. Copyright © 2012 Elsevier B.V. All rights reserved.

Nonlocal Poisson-Fermi double-layer models: Effects of nonuniform ion sizes on double-layer structure

NASA Astrophysics Data System (ADS)

Xie, Dexuan; Jiang, Yi

2018-05-01

This paper reports a nonuniform ionic size nonlocal Poisson-Fermi double-layer model (nuNPF) and a uniform ionic size nonlocal Poisson-Fermi double-layer model (uNPF) for an electrolyte mixture of multiple ionic species, variable voltages on electrodes, and variable induced charges on boundary segments. The finite element solvers of nuNPF and uNPF are developed and applied to typical double-layer tests defined on a rectangular box, a hollow sphere, and a hollow rectangle with a charged post. Numerical results show that nuNPF can significantly improve the quality of the ionic concentrations and electric fields generated from uNPF, implying that the effect of nonuniform ion sizes is a key consideration in modeling the double-layer structure.

Estimation of the ionic charge of non-metallic species into an electrical discharge through a web application

NASA Astrophysics Data System (ADS)

Pérez Gutiérrez, B. R.; Vera-Rivera, F. H.; Niño, E. D. V.

2016-08-01

Estimate the ionic charge generated in electrical discharges will allow us to know more accurately the concentration of ions implanted on the surfaces of nonmetallic solids. For this reason, in this research a web application was developed to allow us to calculate the ionic charge generated in an electrical discharge from the experimental parameters established in an ion implantation process performed in the JUPITER (Joint Universal Plasma and Ion Technologies Experimental Reactor) reactor. The estimated value of the ionic charge will be determined from data acquired on an oscilloscope, during startup and shutdown of electrical discharge, which will then be analyzed and processed. The study will provide best developments with regard to the application of ion implantation in various industrial sectors.

Lewis Acidic Ionic Liquids.

PubMed

Brown, Lucy C; Hogg, James M; Swadźba-Kwaśny, Małgorzata

2017-08-21

Until very recently, the term Lewis acidic ionic liquids (ILs) was nearly synonymous with halometallate ILs, with a strong focus on chloroaluminate(III) systems. The first part of this review covers the historical context in which these were developed, speciation of a range of halometallate ionic liquids, attempts to quantify their Lewis acidity, and selected recent applications: in industrial alkylation processes, in supported systems (SILPs/SCILLs) and in inorganic synthesis. In the last decade, interesting alternatives to halometallate ILs have emerged, which can be divided into two sub-sections: (1) liquid coordination complexes (LCCs), still based on halometallate species, but less expensive and more diverse than halometallate ionic liquids, and (2) ILs with main-group Lewis acidic cations. The two following sections cover these new liquid Lewis acids, also highlighting speciation studies, Lewis acidity measurements, and applications.

A computer program for geochemical analysis of acid-rain and other low-ionic-strength, acidic waters

USGS Publications Warehouse

Johnsson, P.A.; Lord, D.G.

1987-01-01

ARCHEM, a computer program written in FORTRAN 77, is designed primarily for use in the routine geochemical interpretation of low-ionic-strength, acidic waters. On the basis of chemical analyses of the water, and either laboratory or field determinations of pH, temperature, and dissolved oxygen, the program calculates the equilibrium distribution of major inorganic aqueous species and of inorganic aluminum complexes. The concentration of the organic anion is estimated from the dissolved organic concentration. Ionic ferrous iron is calculated from the dissolved oxygen concentration. Ionic balances and comparisons of computed with measured specific conductances are performed as checks on the analytical accuracy of chemical analyses. ARCHEM may be tailored easily to fit different sampling protocols, and may be run on multiple sample analyses. (Author 's abstract)

High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

How ionic species structure influences phase structure and transitions from protic ionic liquids to liquid crystals to crystals.

PubMed

Greaves, Tamar L; Broomhall, Hayden; Weerawardena, Asoka; Osborne, Dale A; Canonge, Bastien A; Drummond, Calum J

2017-12-14

The phase behaviour of n-alkylammonium (C6 to C16) nitrates and formates has been characterised using synchrotron small angle and wide angle X-ray scattering (SAXS/WAXS), differential scanning calorimetry (DSC), cross polarised optical microscopy (CPOM) and Fourier transform infrared spectroscopy (FTIR). The protic salts may exist as crystalline, liquid crystalline or ionic liquid materials depending on the alkyl chain length and temperature. n-Alkylammonium nitrates with n ≥ 6 form thermotropic liquid crystalline (LC) lamellar phases, whereas n ≥ 8 was required for the formate series to form this LC phase. The protic ionic liquid phase showed an intermediate length scale nanostructure resulting from the segregation of the polar and nonpolar components of the ionic liquid. This segregation was enhanced for longer n-alkyl chains, with a corresponding increase in the correlation length scale. The crystalline and liquid crystalline phases were both lamellar. Phase transition temperatures, lamellar d-spacings, and liquid correlation lengths for the n-alkylammonium nitrates and formates were compared with those for n-alkylammonium chlorides and n-alkylamines. Plateau regions in the liquid crystalline to liquid phase transition temperatures as a function of n for the n-alkylammonium nitrates and formates are consistent with hydrogen-bonding and cation-anion interactions between the ionic species dominating alkyl chain-chain van der Waals interactions, with the exception of the mid chained hexyl- and heptylammonium formates. The d-spacings of the lamellar phases for both the n-alkylammonium nitrates and formates were consistent with an increase in chain-chain layer interdigitation within the bilayer-based lamellae with increasing alkyl chain length, and they were comparable to the n-alkylammonium chlorides.

Theoretical Study of Renewable Ionic Liquids in the Pure State and with Graphene and Carbon Nanotubes.

PubMed

García, Gregorio; Atilhan, Mert; Aparicio, Santiago

2015-09-17

The N-ethyl-N-(furan-2-ylmethyl)ethanaminium dihydrogen phosphate ionic liquid was studied as a model of ionic liquids which can be produced from totally renewable sources. A computational study using both molecular dynamics and density functional theory methods was carried out. The properties, structuring, and intermolecular interactions (hydrogen bonding) of this fluid in the pure state were studied as a function of pressure and temperature. Likewise, the adsorption on graphene and the confinement between graphene sheets was also studied. The solvation of single walled carbon nanotubes in the selected ionic liquid was analyzed together with the behavior of ions confined inside these nanotubes. The reported results show remarkable properties for this fluid, which show that many of the most relevant properties of ionic liquids and their ability to interact with carbon nanosystems may be maintained and even improved using new families of renewable compounds instead of classic types of ionic liquids with worse environmental, toxicological, and economical profiles.

Radiation-Induced Damage to Nucleic Acid Constituents

NASA Astrophysics Data System (ADS)

Kim, Heasook

The objective of this research was to identify the primary free radical species produced by ionizing radiation in DNA. The ultimate goal would be to use these data obtained from model compounds to analyze radiation-induced damage in DNA itself. The different single crystals were studied in detail. The first was the sodium salt of guanosine-3 ^':5^' -cyclic monophosphate (cyclic GMP). The results of studies on crystals irradiated at 4.2^ circK distinguished two species. One of these species exhibited a non-exchangeable proton coupling that was characterized by ENDOR spectroscopy and shown to be sigma proton. The spin density on C8 was deduced from the ENDOR hyperfine coupling tensor and found to be 0.15. The second species also exhibited a non-exchangeable sigma proton coupling and a beta proton coupling. The spin densities on C8 and N9 were deduced from ENDOR measurements to be 0.09 and 0.36. The former is attributed to the oxidation product and the latter to the primary reduction product. These products are respectively the guanine cation and anion. The second single crystal studied was a sodium salt of 2^'-deoxyguanosine -5^'-monophosphate tetrahydrate. The ESR and ENDOR spectra obtained from this crystal after x-irradiation at 4.2^circK were complex and the paramagnetic species were tentatively identified as ionic species. The third DNA model compound studied was thymidine. Single crystal of thymidine were irradiated at 1.6^ circK and at 4.2^circ K. The lower temperature preserved a more primitive stage of the radiation damage process. ENDOR measurements distinguished three paramagnetic species. The most interesting component of the paramagnetic absorption in crystals irradiated at 1.6^circK is attributed to trapped electron. These electrons are stabilized by the electrostatic fields generated by hydroxy dipoles. The hyperfine couplings between the trapped electron and the proton of these polar groups were deduced from ENDOR measurements. The ESR and ENDOR measurements described in this report were carried out DNA model compounds x-irradiated and measured at lower temperatures than reported previously. The experiments have demonstrated that an earlier stage of radiation damage can sometimes be stabilized and characterized in single crystals by maintaining the sample at 1.4 ^circK. (Abstract shortened with permission of author.).

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.

Growth-induced anisotropy in bismuth - Rare-earth iron garnets

NASA Technical Reports Server (NTRS)

Fratello, V. J.; Slusky, S. E. G.; Brandle, C. D.; Norelli, M. P.

1986-01-01

The bismuth-doped rare-earth iron garnets, (R3-x-yBixPby)Fe5O12 (Bi:RIG, R = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), were prepared under constant growth conditions to investigate the influence of ionic species on the bismuth-based growth-induced uniaxial anisotropy K(u) exp g. The effect of ionic species on growth-induced anisotropy in Bi:RIG was not consistent with the ionic size model of site ordering. In particular, Bi:SmIG, Bi:EuIG, and Bi:TbIG displayed high growth-induced anisotropies, up to 331,000 erg/cu cm at room temperature for x of about 0.5. The temperature dependence of these K(u) exp gs was somewhat higher than that of the well studied Bi:YIG. The site ordering of Bi can be modeled by assuming that small, low-oxygen-coordination BiOw exp +3-2 w melt complexes have a strong site selectivity for small, high-oxygen coordination sites at the growth interface.

Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids

NASA Astrophysics Data System (ADS)

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards ‘single-layer’ graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml-1, and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Vaporisation of a dicationic ionic liquid.

PubMed

Lovelock, Kevin R J; Deyko, Alexey; Corfield, Jo-Anne; Gooden, Peter N; Licence, Peter; Jones, Robert G

2009-02-02

Highest heat of vaporization yet: The dicationic ionic liquid [C(3)(C(1)Im)(2)][Tf(2)N](2) evaporates as a neutral ion triplet. These neutral ion triplets can then be ionised to form singly and doubly charged ions. The mass spectrum exhibits the dication attached to one remaining anion, and the naked dication itself (see picture).

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.

Dynamic ultrasonic nebulisation extraction coupled with headspace ionic liquid-based single-drop microextraction for the analysis of the essential oil in Forsythia suspensa.

PubMed

Yang, Jinjuan; Wei, Hongmin; Teng, Xiane; Zhang, Hanqi; Shi, Yuhua

2014-01-01

Ionic liquids have attracted much attention as an extraction solvent instead of traditional organic solvent in single-drop microextraction. However, non-volatile ionic liquids are difficult to couple with gas chromatography. Thus, the following injection system for the determination of organic compounds is described. To establish an environmentally friendly, simple, and effective extraction method for preparation and analysis of the essential oil from aromatic plants. The dynamic ultrasonic nebulisation extraction was coupled with headspace ionic liquid-based single-drop microextraction(UNE-HS/IL/SDME)for the extraction of essential oils from Forsythia suspense fruits. After 13 min of extraction for 50 mg sample, the extracts in ionic liquid were evaporated rapidly in the gas chromatography injector through a thermal desorption unit (5 s). The traditional extraction method was carried out for comparative study. The optimum conditions were: 3 μL of 1-methyl-3-octylimidazolium hexafluorophosphate was selected as the extraction solvent, the sample amount was 50 mg, the flow rate of purging gas was 200 mL/min, the extraction time was 13 min, the injection volume was 2 μL, and the thermal desorption temperature and time were 240 °C and 5 s respectively. Comparing with hydrodistillation (HD), the proposed method was environment friendly and efficient. The proposed method is environmentally friendly, time saving, with high efficiency and low consumption. It would extend the application range of the HS/SDME and would be useful especially for aromatic plants analysis. Copyright © 2013 John Wiley & Sons, Ltd.

Ultralow percolation threshold of single walled carbon nanotube-epoxy composites synthesized via an ionic liquid dispersant/initiator

NASA Astrophysics Data System (ADS)

Watters, Arianna L.; Palmese, Giuseppe R.

2014-09-01

Uniform dispersion of single walled carbon nanotubes (SWNTs) in an epoxy was achieved by a streamlined mechano-chemical processing method. SWNT-epoxy composites were synthesized using a room temperature ionic liquid (IL) with an imidazolium cation and dicyanamide anion. The novel approach of using ionic liquid that behaves as a dispersant for SWNTs and initiator for epoxy polymerization greatly simplifies nanocomposite synthesis. The material was processed using simple and scalable three roll milling. The SWNT dispersion of the resultant composite was evaluated by electron microscopy and electrical conductivity measurements in conjunction with percolation theory. Processing conditions were optimized to achieve the lowest possible percolation threshold, 4.29 × 10-5 volume fraction SWNTs. This percolation threshold is among the best reported in literature yet it was obtained using a streamlined method that greatly simplifies processing.

Drag reducing properties of microalgal exopolymers.

PubMed

Ramus, J; Kenney, B E; Shaughnessy, E J

1989-01-25

Dilute aqueous solutions of polymers released by marine phytoplankton (microalgae) were shown to effectively reduce drag in capillary pipe flow. Tests were performed in a capillary turbulent flow viscometer which extruded small samples under high pressures. In all, 22 species were screened, and the products of one chlorophyte and four rhodophyte species proved especially effective. The viscoelastic polymers produced by these species delayed the transition from laminar to turbulent flow to significantly higher Re. In general, polymeric regime segments come off the maximum drag reduction asymptote at characteristic retro-onset points, and come to lie approximately parallel to, but displaced upwards from the Prandtl-von Karman line. The delay to transition was shown to be dependent on additive polymer concentration, capillary diameter, and temperature. Ionic concentration, ionic composition, or pH had little effect on drag reducing properties.

Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

PubMed

Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

2015-12-28

A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect.

Ionomer Design, Synthesis and Characterization for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph H.

2013-03-01

For ionic actuators and battery separators, it is vital to utilize single-ion conductors that avoid the detrimental polarization of other ions; the commonly studied dual-ion conductors simply will not be used in the next generation of materials for these applications. Ab initio quantum chemistry calculations at 0 K in vacuum characterize ion interactions and ion solvation by various functional groups, allowing identification of constituents with weak interactions to be incorporated in ionomers for facile ion transport. Simple ideas for estimating the ion interactions and solvation at practical temperatures and dielectric constants are presented that indicate the rank ordering observed at 0 K in vacuum should be preserved. Hence, such ab initio calculations are useful for screening the plethora of combinations of polymer-ion, counterion and polar functional groups, to decide which are worthy of synthesis for new ionomers. Single-ion conducting ionomers are synthesized based on these calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for ionic actuators and battery separators. Characterization by X-ray scattering, dielectric spectroscopy, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. Examples are shown of how ab initio calculations can be used to understand experimental observations of dielectric constant, glass transition temperature and conductivity of polymerized ionic liquids with counterions being either lithium, sodium, fluoride, hydroxide (for batteries) or bulky ionic liquids (for ionic actuators). This work was supported by the Department of Energy under Grant BES-DE-FG02-07ER46409.

Critical predicted no effect concentrations (PNECs) should not be based on a single toxicity test.

PubMed

Chapman, Peter M; Elphick, James R

2015-05-01

Predicted no-effect concentrations (PNECs), which represent the concentration of a substance below which an unacceptable effect most likely will not occur, are widely used for risk assessment and in environmental policy and regulation. They are typically based on single-species laboratory toxicity tests; often, a single test result for the most sensitive endpoints drives the derivation of a PNEC. In the present study, the authors provide a case study emphasizing the importance of determining the reliability of those most sensitive endpoints. Five 21-d Daphnia magna toxicity tests conducted using the same procedures by 2 laboratories gave 20% inhibitory concentration responses to a specific ionic composition of total dissolved solids that varied from 684 mg/L to more than 1510 mg/L. The concentration-response curve was shallow; thus, these differences could have been attributable to chance alone. The authors strongly recommend that the most sensitive endpoints that determine PNECs not be based on a single toxicity test result but rather on the geometric mean of at least 3 test results to adequately assess and bound test variability, especially when the concentration-response curve is shallow. © 2015 SETAC.

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

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

Size and Charge Dependence of Ion Transport in Human Nail Plate.

PubMed

Baswan, Sudhir M; Li, S Kevin; LaCount, Terri D; Kasting, Gerald B

2016-03-01

The electrical properties of human nail plate are poorly characterized yet are a key determinate of the potential to treat nail diseases, such as onychomycosis, using iontophoresis. To address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of -1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were 3-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upward of 5 Å (molecular weight, ca. ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Influence of ionic liquid and ionic salt on protein against the reactive species generated using dielectric barrier discharge plasma.

PubMed

Attri, Pankaj; Sarinont, Thapanut; Kim, Minsup; Amano, Takaaki; Koga, Kazunori; Cho, Art E; Choi, Eun Ha; Shiratani, Masaharu

2015-12-10

The presence of salts in biological solution can affect the activity of the reactive species (RS) generated by plasma, and so they can also have an influence on the plasma-induced sterilization. In this work, we assess the influence that diethylammonium dihydrogen phosphate (DEAP), an ionic liquid (IL), and sodium chloride (NaCl), an ionic salt (IS), have on the structural changes in hemoglobin (Hb) in the presence of RS generated using dielectric barrier discharge (DBD) plasma in the presence of various gases [O2, N2, Ar, He, NO (10%) + N2 and Air]. We carry out fluorescence spectroscopy to verify the generation of (•)OH with or without the presence of DEAP IL and IS, and we use electron spin resonance (ESR) to check the generation of H(•) and (•)OH. In addition, we verified the structural changes in the Hb structure after treatment with DBD in presence and absence of IL and IS. We then assessed the structural stability of the Hb in the presence of IL and IS by using molecular dynamic (MD) simulations. Our results indicate that the IL has a strong effect on the conservation of the Hb structure relative to that of IS against RS generated by plasma.

Influence of ionic liquid and ionic salt on protein against the reactive species generated using dielectric barrier discharge plasma

NASA Astrophysics Data System (ADS)

Attri, Pankaj; Sarinont, Thapanut; Kim, Minsup; Amano, Takaaki; Koga, Kazunori; Cho, Art E.; Ha Choi, Eun; Shiratani, Masaharu

2015-12-01

The presence of salts in biological solution can affect the activity of the reactive species (RS) generated by plasma, and so they can also have an influence on the plasma-induced sterilization. In this work, we assess the influence that diethylammonium dihydrogen phosphate (DEAP), an ionic liquid (IL), and sodium chloride (NaCl), an ionic salt (IS), have on the structural changes in hemoglobin (Hb) in the presence of RS generated using dielectric barrier discharge (DBD) plasma in the presence of various gases [O2, N2, Ar, He, NO (10%) + N2 and Air]. We carry out fluorescence spectroscopy to verify the generation of •OH with or without the presence of DEAP IL and IS, and we use electron spin resonance (ESR) to check the generation of H• and •OH. In addition, we verified the structural changes in the Hb structure after treatment with DBD in presence and absence of IL and IS. We then assessed the structural stability of the Hb in the presence of IL and IS by using molecular dynamic (MD) simulations. Our results indicate that the IL has a strong effect on the conservation of the Hb structure relative to that of IS against RS generated by plasma.

Improving the light-emitting properties of single-layered polyfluorene light-emitting devices by simple ionic liquid blending

NASA Astrophysics Data System (ADS)

Horike, Shohei; Nagaki, Hiroto; Misaki, Masahiro; Koshiba, Yasuko; Morimoto, Masahiro; Fukushima, Tatsuya; Ishida, Kenji

2018-03-01

This paper describes an evaluation of ionic liquids (ILs) as potential electrolytes for single-layered light-emitting devices with good emission performance. As optoelectronic devices continue to grow in abundance, high-performance light-emitting devices with a single emission layer are becoming increasingly important for low-cost production. We show that a simple technique of osmosing IL into the polymer layer can result in high luminous efficiency and good response times of single-layered light-emitting polymers, even without the additional stacking of charge carrier injection and transport layers. The IL contributions to the light-emission of the polymer are discussed from the perspectives of energy diagrams and of the electric double layers on the electrodes. Our findings enable a faster, cheaper, and lower-in-waste production of light-emitting devices.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

New applications in EPA’s ECOTOX Knowledge System: Assimilating relative potencies of metals across chemical and biological species from literature-based toxicity effects data.

EPA Science Inventory

Toxicity of metals in field settings can vary widely among ionic chemical species and across biological receptors. Thus, a challenge often found in developing TRVs for the risk assessment of metals is identifying the most appropriate metal and biological species combinations for...

Investigation of secondary school, undergraduate, and graduate learners' mental models of ionic bonding

NASA Astrophysics Data System (ADS)

Coll, Richard K.; Treagust, David F.

2003-05-01

Secondary school, undergraduate, and graduate level learners' mental models of bonding in ionic substances were explored using an interview protocol that involved the use of physical substances and a focus card containing depictions of ionic bonding and structure. Teachers and faculty from the teaching institutions were interviewed to contextualize teaching models within the educational setting for the inquiry. These data resulted in two socially negotiated consensus teaching models and a series of criterial attributes for these models: the essential qualities, all of which must be negotiated, if the model is used in a way that is acceptable to scientists. The secondary school learners see ionic bonding as consisting of attraction of oppositely charged species that arise from the transfer of electrons driven by the desire of atoms to obtain an octet of electrons. The undergraduates see the lattice structure as a key component of ionic substances and quickly identified specific ionic lattices for the physical prompts used as probes. The graduates also identified strongly with ionic lattices, were less likely to focus on particular ionic structures, and had a stronger appreciation for the notion of the ionic-covalent continuum. The research findings suggest that learners at all educational levels harbor a number of alternative conceptions and prefer to use simple mental models. These findings suggest that teachers and university faculty need to provide stronger links between the detailed nature of a model and its intended purpose.

Extraction and Chromatographic Determination of Shikimic Acid in Chinese Conifer Needles with 1-Benzyl-3-methylimidazolium Bromide Ionic Liquid Aqueous Solutions

PubMed Central

Chen, Fengli; Hou, Kexin; Li, Shuangyang; Zu, Yuangang; Yang, Lei

2014-01-01

An ionic liquids-based ultrasound-assisted extraction (ILUAE) method was successfully developed for extracting shikimic acid from conifer needles. Eleven 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were investigated and 1-benzyl-3-methylimidazolium bromide solution was selected as the solvent. The conditions for ILUAE, including the ionic liquid concentration, ultrasound power, ultrasound time, and liquid-solid ratio, were optimized. The proposed method had good recovery (99.37%–100.11%) and reproducibility (RSD, n = 6; 3.6%). ILUAE was an efficient, rapid, and simple sample preparation technique that showed high reproducibility. Based on the results, a number of plant species, namely, Picea koraiensis, Picea meyeri, Pinus elliottii, and Pinus banksiana, were identified as among the best resources of shikimic acid. PMID:24782942

The toxic Doppelganger: on the ionic and molecular mimicry of cadmium.

PubMed

Chmielowska-Bąk, Jagna; Izbiańska, Karolina; Deckert, Joanna

2013-01-01

Cadmium is a toxic heavy metal which can cause numerous alterations in cell functioning. Exposure to cadmium leads to generation of reactive oxygen species, disorders in membrane structure and functioning, inhibition of respiration, disturbances in ion homeostasis, perturbations in cell division, and initiation of apoptosis and necrosis. This heavy metal is considered a carcinogen by the Agency for Toxic Substances and Disease Registry. At least some of the described toxic effects could result from the ability of cadmium to mimic other divalent ions and alert signal transduction networks. This review describes the role of cadmium mimicry in its uptake, reactive oxygen species generation, alterations in calmodulin, Wnt/β-catenin and estrogen signaling pathways, and modulation of neurotransmission. The last section is dedicated to the single known case of a favorable function performed by cadmium mimicry: marine diatoms, which live in zinc deficient conditions, utilize cadmium as a cofactor in carbonic anhydrase - so far the only described cadmium enzyme.

Precipitation of thin-film organic single crystals by a novel crystal growth method using electrospray and ionic liquid film

NASA Astrophysics Data System (ADS)

Ueda, Hiroyuki; Takeuchi, Keita; Kikuchi, Akihiko

2018-04-01

We report an organic single crystal growth technique, which uses a nonvolatile liquid thin film as a crystal growth field and supplies fine droplets containing solute from the surface of the liquid thin film uniformly and continuously by electrospray deposition. Here, we investigated the relationships between the solute concentration of the supplied solution and the morphology and size of precipitated crystals for four types of fluorescent organic low molecule material [tris(8-hydroxyquinoline)aluminum (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), N,N‧-bis(3-methylphenyl)-N,N‧-diphenylbenzidine (TPD), and N,N-bis(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB)] using an ionic liquid as the nonvolatile liquid. As the concentration of the supplied solution decreased, the morphology of precipitated crystals changed from dendritic or leaf shape to platelike one. At the solution concentration of 0.1 mg/ml, relatively large platelike single crystals with a diagonal length of over 100 µm were obtained for all types of material. In the experiment using ionic liquid and dioctyl sebacate as nonvolatile liquids, it was confirmed that there is a clear positive correlation between the maximum volume of the precipitated single crystal and the solubility of solute under the same solution supply conditions.

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, Anthony J.; Barlow, Stephan E.

1999-01-01

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap's ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a "gentle" environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species.

Instrumentation for low noise nanopore-based ionic current recording under laser illumination

NASA Astrophysics Data System (ADS)

Roelen, Zachary; Bustamante, José A.; Carlsen, Autumn; Baker-Murray, Aidan; Tabard-Cossa, Vincent

2018-01-01

We describe a nanopore-based optofluidic instrument capable of performing low-noise ionic current recordings of individual biomolecules under laser illumination. In such systems, simultaneous optical measurements generally introduce significant parasitic noise in the electrical signal, which can severely reduce the instrument sensitivity, critically hindering the monitoring of single-molecule events in the ionic current traces. Here, we present design rules and describe simple adjustments to the experimental setup to mitigate the different noise sources encountered when integrating optical components to an electrical nanopore system. In particular, we address the contributions to the electrical noise spectra from illuminating the nanopore during ionic current recording and mitigate those effects through control of the illumination source and the use of a PDMS layer on the SiNx membrane. We demonstrate the effectiveness of our noise minimization strategies by showing the detection of DNA translocation events during membrane illumination with a signal-to-noise ratio of ˜10 at 10 kHz bandwidth. The instrumental guidelines for noise minimization that we report are applicable to a wide range of nanopore-based optofluidic systems and offer the possibility of enhancing the quality of synchronous optical and electrical signals obtained during single-molecule nanopore-based analysis.

Effects of ionic strength on passive and iontophoretic transport of cationic permeant across human nail.

PubMed

Smith, Kelly A; Hao, Jinsong; Li, S Kevin

2009-06-01

Transport across the human nail under hydration can be modeled as hindered transport across aqueous pore pathways. As such, nail permselectivity to charged species can be manipulated by changing the ionic strength of the system in transungual delivery to treat nail diseases. The present study investigated the effects of ionic strength upon transungual passive and iontophoretic transport. Transungual passive and anodal iontophoretic transport experiments of tetraethylammonium ion (TEA) were conducted under symmetric conditions in which the donor and receiver had the same ionic strength in vitro. Experiments under asymmetric conditions were performed to mimic the in vivo conditions. Prior to the transport studies, TEA uptake studies were performed to assess the partitioning of TEA into the nail. Permselectivity towards TEA was inversely related to ionic strength in both passive and iontophoretic transport. The permeability and transference number of TEA were higher at lower ionic strengths under the symmetric conditions due to increased partitioning of TEA into the nail. Transference numbers were smaller under the asymmetric conditions compared with their symmetric counterparts. The results demonstrate significant ionic strength effects upon the partitioning and transport of a cationic permeant in transungual transport, which may be instrumental in the development of transungual delivery systems.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Confirmation of Soluble Sulfate at the Phoenix Landing Site: Implications for Martian Geochemistry and Habitability

NASA Technical Reports Server (NTRS)

Kounaves, S. P.; Hecht, M. H.; Kapit, J.; Quinn, R. C.; Catling, D. C.; Clark, B. C.; Ming, D. W.; Gospodinova, K.; Hredzak, P.; McElhoney, K.;

Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity

DOE PAGES

Cantu, David C.; Lee, Juntaek; Lee, Mal -Soon; ...

2016-03-28

The deployment of transformational non-aqueous CO 2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO 2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO 2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO 2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, thismore » work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO 2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.« less

Intrinsic electric fields and proton diffusion in immobilized protein membranes. Effects of electrolytes and buffers.

PubMed Central

Zabusky, N J; Deem, G S

1979-01-01

We present a theory for proton diffusion through an immobilized protein membrane perfused with an electrolyte and a buffer. Using a Nernst-Planck equation for each species and assuming local charge neutrality, we obtain two coupled nonlinear diffusion equations with new diffusion coefficients dependent on the concentration of all species, the diffusion constants or mobilities of the buffers and salts, the pH-derivative of the titration curves of the mobile buffer and the immobilized protein, and the derivative with respect to ionic strength of the protein titration curve. Transient time scales are locally pH-dependent because of protonation-deprotonation reactions with the fixed protein and are ionic strength-dependent because salts provide charge carriers to shield internal electric fields. Intrinsic electric fields arise proportional to the gradient of an "effective" charge concentration. The field may reverse locally if buffer concentrations are large (greater to or equal to 0.1 M) and if the diffusivity of the electrolyte species is sufficiently small. The "ideal" electrolyte case (where each species has the same diffusivity) reduces to a simple form. We apply these theoretical considerations to membranes composed of papain and bovine serum albumin (BSA) and show that intrinsic electric fields greatly enhance the mobility of protons when the ionic strength of the salts is smaller than 0.1 M. These results are consistent with experiments where pH changes are observed to depend strongly on buffer, salt, and proton concentrations in baths adjacent to the membranes. PMID:233570

Inorganic ion composition in Tardigrada: cryptobionts contain a large fraction of unidentified organic solutes.

PubMed

Halberg, Kenneth Agerlin; Larsen, Kristine Wulff; Jørgensen, Aslak; Ramløv, Hans; Møbjerg, Nadja

2013-04-01

Many species of tardigrades are known to tolerate extreme environmental stress, yet detailed knowledge of the mechanisms underlying the remarkable adaptations of tardigrades is still lacking, as are answers to many questions regarding their basic biology. Here, we present data on the inorganic ion composition and total osmotic concentration of five different species of tardigrades (Echiniscus testudo, Milnesium tardigradum, Richtersius coronifer, Macrobiotus cf. hufelandi and Halobiotus crispae) using high-performance liquid chromatography and nanoliter osmometry. Quantification of the ionic content indicates that Na(+) and Cl(-) are the principal inorganic ions in tardigrade fluids, albeit other ions, i.e. K(+), NH4(+), Ca(2+), Mg(2+), F(-), SO4(2-) and PO4(3-) were also detected. In limno-terrestrial tardigrades, the respective ions are concentrated by a large factor compared with that of the external medium (Na(+), ×70-800; K(+), ×20-90; Ca(2+) and Mg(2+), ×30-200; F(-), ×160-1040, Cl(-), ×20-50; PO4(3-), ×700-2800; SO4(2-), ×30-150). In contrast, in the marine species H. crispae, Na(+), Cl(-) and SO4(2-) are almost in ionic equilibrium with (brackish) salt water, while K(+), Ca(2+), Mg(2+) and F(-) are only slightly concentrated (×2-10). An anion deficit of ~120 mEq l(-1) in M. tardigradum and H. crispae indicates the presence of unidentified ionic components in these species. Body fluid osmolality ranges from 361±49 mOsm kg(-1) in R. coronifer to 961±43 mOsm kg(-1) in H. crispae. Concentrations of most inorganic ions are largely identical between active and dehydrated groups of R. coronifer, suggesting that this tardigrade does not lose large quantities of inorganic ions during dehydration. The large osmotic and ionic gradients maintained by both limno-terrestrial and marine species are indicative of a powerful ion-retentive mechanism in Tardigrada. Moreover, our data indicate that cryptobiotic tardigrades contain a large fraction of unidentified organic osmolytes, the identification of which is expected to provide increased insight into the phenomenon of cryptobiosis.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2015-12-03

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

A Water Dissolvable Electrolyte with an Ionic Liquid for Eco-Friendly Electronics.

PubMed

Yamada, Shunsuke; Toshiyoshi, Hiroshi

2018-06-21

A water-dissolvable electrolyte is developed by combining an ionic liquid (IL) with poly(vinyl alcohol) (PVA), which decays over time by contact with water. An IL generally consists of two species of ions (anion and cation), and forms an electrical double layer (EDL) of a large electrostatic capacitance due to the ions accumulated in the vicinity of a conductive electrode when voltage is applied. In a similar manner, the ionic gel developed in this work forms an EDL due to the ions suspended in the conjugated polymer network while maintaining the gel form. Test measurements show a large capacitance of 13 µF cm -2 within the potential window of the IL. The ionic gel shows an electrical conductance of 20 µS cm -1 due to the ionic conduction, which depends on the weight ratio of the IL with respect to the polymer. The developed ionic gel dissolves into water in 16 h. Potential application includes the electrolyte in disposable electronics such as distributed sensors and energy harvesters that are supposed to be harmless to environment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Extraction and Esterification of Low-Titer Short-Chain Volatile Fatty Acids from Anaerobic Fermentation with Ionic Liquids.

PubMed

Andersen, Stephen J; Berton, Jan K E T; Naert, Pieter; Gildemyn, Sylvia; Rabaey, Korneel; Stevens, Christian V

2016-08-23

Ionic liquids can both act as a solvent and mediate esterification to valorize low-titer volatile fatty acids and generate organic solvents from renewable carbon sources including biowaste and CO2 . In this study, four phosphonium ionic liquids were tested for single-stage extraction of acetic acid from a dilute stream and esterification to ethyl acetate with added ethanol and heat. The esterification proceeded with a maximum conversion of 85.9±1.3 % after 30 min at 75 °C at a 1:1 stoichiometric ratio of reactants. Extraction and esterification can be tailored using mixed-anion ionic liquids; this is demonstrated herein using a common trihexyl(tetradecyl)phosphonium cation and a mixed chloride and bis(trifluoromethylsulfonyl)imide anion ionic liquid. As a further proof-of-concept, ethyl acetate was generated from an ionic liquid-driven esterification of an acetic acid extractant generated using CO2 as the only carbon source by microbial electrosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron Requirement and Iron Uptake from Various Iron Compounds by Different Plant Species

PubMed Central

Christ, Rudolf A.

1974-01-01

The Fe requirements of four monocotyledonous plant species (Avena sativa L., Triticum aestivum L., Oryza sativa L., Zea mays L.) and of three dicotyledonous species (Lycopersicum esculentum Mill., Cucumis sativus L., Glycine maxima (L.) Merr.) in hydroponic cultures were ascertained. Fe was given as NaFe-EDDHA chelate (Fe ethylenediamine di (O-hydroxyphenylacetate). I found that the monocotyledonous species required a substantially higher Fe concentration in the nutrient solution in order to attain optimum growth than did the dicotyledonous species. Analyses showed that the process of iron uptake was less efficient with the monocotyledonous species. When the results obtained by using chelated Fe were compared with those using ionic Fe, it was shown that the inefficient species were equally inefficient in utilizing Fe3+ ions. However, the differences between the efficient and the inefficient species disappeared when Fe2+ was used. This confirms the work of others who postulated that Fe3+ is reduced before uptake of chelated iron by the root. In addition, it was shown that reduction also takes place when Fe is used in ionic form. The efficiency of Fe uptake seems to depend on the efficiency of the root system of the particular plant species in reducing Fe3+. The removal of Fe from the chelate complex after reduction to Fe2+ seems to present no difficulties to the various plant species. PMID:16658933

Micro-rheology on (polymer-grafted) colloids using optical tweezers.

PubMed

Gutsche, C; Elmahdy, M M; Kegler, K; Semenov, I; Stangner, T; Otto, O; Ueberschär, O; Keyser, U F; Krueger, M; Rauscher, M; Weeber, R; Harting, J; Kim, Y W; Lobaskin, V; Netz, R R; Kremer, F

2011-05-11

Optical tweezers are experimental tools with extraordinary resolution in positioning (± 1 nm) a micron-sized colloid and in the measurement of forces (± 50 fN) acting on it-without any mechanical contact. This enables one to carry out a multitude of novel experiments in nano- and microfluidics, of which the following will be presented in this review: (i) forces within single pairs of colloids in media of varying concentration and valency of the surrounding ionic solution, (ii) measurements of the electrophoretic mobility of single colloids in different solvents (concentration, valency of the ionic solution and pH), (iii) similar experiments as in (i) with DNA-grafted colloids, (iv) the nonlinear response of single DNA-grafted colloids in shear flow and (v) the drag force on single colloids pulled through a polymer solution. The experiments will be described in detail and their analysis discussed.

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

On the heterogeneity of fluorescence lifetime of room temperature ionic liquids: onset of a journey for exploring red emitting dyes.

PubMed

Ghosh, Anup; Chatterjee, Tanmay; Mandal, Prasun K

2012-06-25

An excitation and emission wavelength dependent non-exponential fluorescence decay behaviour of room temperature ionic liquids (RTILs) has been noted. Average fluorescence lifetimes have been found to vary by a factor of three or more. Red emitting dyes dissolved in RTILs are found to follow hitherto unobserved single exponential fluorescence decay behaviour.

Room temperature electrodeposition of actinides from ionic solutions

DOEpatents

Hatchett, David W.; Czerwinski, Kenneth R.; Droessler, Janelle; Kinyanjui, John

2017-04-25

Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.

Charge-tagged ligands: useful tools for immobilising complexes and detecting reaction species during catalysis

PubMed Central

Limberger, Jones; Leal, Bárbara C.; Monteiro, Adriano L.

2015-01-01

In recent years, charge-tagged ligands (CTLs) have become valuable tools in organometallic catalysis. Insertion of an ionic side chain into the molecular skeleton of a known ligand has become a useful protocol for anchoring ligands, and consequently catalysts, in polar and ionic liquid phases. In addition, the insertion of a cationic moiety into a ligand is a powerful tool that can be used to detect reaction intermediates in organometallic catalysis through electrospray ionisation mass spectrometry (ESI-MS) experiments. The insertion of an ionic tag ensures the charge in the intermediates independently of the ESI-MS. For this reason, these ligands have been used as ionic probes in mechanistic studies for several catalytic reactions. Here, we summarise selected examples on the use of CTLs as immobilising agents in organometallic catalysis and as probes for studying mechanisms through ESI-MS. PMID:28553458

Simultaneous Ionic Current and Potential Detection of Nanoparticles by a Multifunctional Nanopipette.

PubMed

Panday, Namuna; Qian, Gongming; Wang, Xuewen; Chang, Shuai; Pandey, Popular; He, Jin

2016-12-27

Nanopore sensing-based technologies have made significant progress for single molecule and single nanoparticle detection and analysis. In recent years, multimode sensing by multifunctional nanopores shows the potential to greatly improve the sensitivity and selectivity of traditional resistive-pulse sensing methods. In this paper, we showed that two label-free electric sensing modes could work cooperatively to detect the motion of 40 nm diameter spherical gold nanoparticles (GNPs) in solution by a multifunctional nanopipette. The multifunctional nanopipettes containing both nanopore and nanoelectrode (pyrolytic carbon) at the tip were fabricated quickly and cheaply. We demonstrated that the ionic current and local electrical potential changes could be detected simultaneously during the translocation of individual GNPs. We also showed that the nanopore/CNE tip geometry enabled the CNE not only to detect the translocation of single GNP but also to collectively detect several GNPs outside the nanopore entrance. The dynamic accumulation of GNPs near the nanopore entrance resulted in no detectable current changes, but was detected by the potential changes at the CNE. We revealed the motions of GNPs both outside and inside the nanopore, individually and collectively, with the combination of ionic current and potential measurements.

Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

PubMed

Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

2007-01-01

The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

Resistive sensing of gaseous nitrogen dioxide using a dispersion of single-walled carbon nanotubes in an ionic liquid

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

Mishra, Prabhash; Department of Nanoengineering, Samara State Aerospace University, 443086 Samara; Pavelyev, V.S.

2016-06-15

Graphical abstract: Ionic liquid ([C6-mim]PF6) used as dispersant agent for SWCNTs: An investigations were carried out to find the structural quality and surface modification for sensor application. - Highlights: • An effective technique based on Ionic liquids (IL) and their use as a dispersant. • Electron microscopy and spectroscopy for structure characterization. • Covalent linkage of ILs with SWNTs and dispersion of SWCNTs. • The IL-wrapped sensing film, capable for detecting trace levels of gas. - Abstract: Single-walled carbon nanotubes (SWCNTs) were dispersed in an imidazolium-based ionic liquid (IL) and investigated in terms of structural quality, surface functionalization and inter-CNTmore » force. Analysis by field emission electron microscopy and transmission electron microscopy shows the IL layer to coat the SWNTs, and FTIR and Raman spectroscopy confirm strong binding of the ILs to the SWNTs. Two kinds of resistive sensors were fabricated, one by drop casting of IL-wrapped SWCNTs, the other by conventional dispersion of SWCNTs. Good response and recovery to NO{sub 2} is achieved with the IL-wrapped SWCNTs material upon UV-light exposure, which is needed because decrease the desorption energy barrier to increase the gas molecule desorption. NO{sub 2} can be detected in the 1–20 ppm concentration range. The sensor is not interfered by humidity due to the hydrophobic tail of PF6 (ionic liquid) that makes our sensor highly resistant to moisture.« less

Assessing Electrolyte Transport Properties with Molecular Dynamics

DOE PAGES

Jones, R. E.; Ward, D. K.; Gittleson, F. S.; ...

2017-04-15

Here in this work we use estimates of ionic transport properties obtained from molecular dynamics to rank lithium electrolytes of different compositions. We develop linear response methods to obtain the Onsager diffusivity matrix for all chemical species, its Fickian counterpart, and the mobilities of the ionic species. We apply these methods to the well-studied propylene carbonate/ethylene carbonate solvent with dissolved LiBF 4 and O 2. The results show that, over a range of lithium concentrations and carbonate mixtures, trends in the transport coefficients can be identified and optimal electrolytes can be selected for experimental focus; however, refinement of these estimationmore » techniques is necessary for a reliable ranking of a large set of electrolytes.« less

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.

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.

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.

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

2015-10-23

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

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.

Determination of trihalomethanes in waters by ionic liquid-based single drop microextraction/gas chromatographic/mass spectrometry.

PubMed

Aguilera-Herrador, Eva; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

2008-10-31

A simple, rapid, solventless method for the determination of trihalomethanes (THMs) (chloroform, bromodichloromethane, dibromochloromethane and bromoform) in water samples is presented. The analytes are extracted from the headspace of the aqueous matrix into a 2 microL drop of the ionic liquid 1-octyl-3-methyl-imidazolium hexafluorophosphate working at 30 degrees C for 30 min. The separation and detection of the target compounds is accomplished by gas chromatography/mass spectrometry owing to the use of an interface that efficiently transfers the analytes extracted in the ionic liquid drop to the gas chromatograph while preventing the ionic liquid from entering the column. The detection limits obtained are below the values compelled by the legislation, ranging from 0.5 microg L(-1) for chloroform and bromodichloromethane to 0.9 microg L(-1) for dibromochloromethane. The use of ionic liquid in the extraction procedure avoids the use of organic solvents and leads to relative standard deviations that range from 3.1% to 4.8%.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids.

PubMed

DeVine, Jessalyn A; Labib, Marena; Harries, Megan E; Rached, Rouba Abdel Malak; Issa, Joseph; Wishart, James F; Castner, Edward W

2015-08-27

Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime.

Ionization states of helium in He-3-rich solar energetic particle events

NASA Technical Reports Server (NTRS)

Klecker, B.; Hovestadt, D.; Moebius, E.; Scholer, M.; Gloeckler, G.; Ipavich, F. M.

1983-01-01

Results of a systematic study of the ionic charge state of helium in the energy range 0.6-1.0 MeV/nucleon for He-3-rich solar energetic particle events during the time period August 1978 to October 1979 are reported. The data have been obtained with the Max-Planck-Institut/University of Maryland experiment on ISEE-3. Whereas for solar energetic particle events with no enrichment of He-3 relative to He-4 surprisingly large abundances of singly ionized helium have been reported recently, He-3-rich solar energetic particle events do not show significant abundances of He-3(+). This result is consistent with current theories explaining large compositional anomalies by mass per charge dependent selective heating of the minor ion species.

New salts of amino acids with dimeric cations

NASA Astrophysics Data System (ADS)

Ghazaryan, V. V.; Fleck, M.; Petrosyan, A. M.

2010-10-01

Among salts of amino acids there are compounds with the composition 2A..HX, which consist of dimeric A...A+ cations with short symmetric or asymmetric hydrogen bonds between zwitter-ionic and protonated moieties. These species are materials liable to undergo phase transitions or possess interesting nonlinear optical properties. Here, we report the preparation of 20 new salts with dimeric cations from aqueous solutions, including compounds of glycine, betaine, β- alanine, L-alanine, L-phenylalanine, L-threonine, L-valine, L-leucine and L-proline, with BF4-, ClO4-, Cl-, Br-, HSeO3-, and HC2O4-; as anions. The prepared salts are characterized by IR and Raman spectroscopy. Some of them are grown in form of good quality single crystals, which allowed the determination of their crystal structure.

The role of upstream distal electrodes in mitigating electrochemical degradation of ionic liquid ion sources

NASA Astrophysics Data System (ADS)

Brikner, Natalya; Lozano, Paulo C.

2012-11-01

Ionic liquid ion sources produce molecular ions from micro-tip emitters wetted with room-temperature molten salts. When a single ion polarity is extracted, counterions accumulate and generate electrochemical reactions that limit the source lifetime. The dynamics of double layer formation are reviewed and distal electrode contacts are introduced to resolve detrimental electrochemical decomposition effects at the micro-tip apex. By having the emitter follow the ionic liquid potential, operation can be achieved for an extended period of time with no apparent degradation of the material, indicating that electrochemistry can be curtailed and isolated to the upstream distal electrode.

Properties of small Ar sub N-1 K/+/ ionic clusters

NASA Technical Reports Server (NTRS)

Etters, R. D.; Danilowicz, R.; Dugan, J.

1977-01-01

A self-consistent formalism is developed that, based upon a many-body potential, dynamically determines the thermodynamic properties of ionic clusters without an a priori designation of the equilibrium structures. Aggregates consisting of a single closed shell K(+) ion and N-1 isoelectronic argon atoms were studied. The clusters form crystallites at low temperatures, and melting transitions and spontaneous dissociations are indicated. The results confirm experimental evidence that shows that ionic clusters become less stable with increasing N. The crystallite structures formed by four different clusters are isosceles triangle, skewed form, octahedron with ion in the middle, and icosahedron with the ion in the middle.

Quantitative and qualitative optimization of allergen extraction from peanut and selected tree nuts. Part 2. Optimization of buffer and ionic strength using a full factorial experimental design.

PubMed

L'Hocine, Lamia; Pitre, Mélanie

2016-03-01

A full factorial design was used to assess the single and interactive effects of three non-denaturing aqueous (phosphate, borate, and carbonate) buffers at various ionic strengths (I) on allergen extractability from and immunoglobulin E (IgE) immunoreactivity of peanut, almond, hazelnut, and pistachio. The results indicated that the type and ionic strength of the buffer had different effects on protein recovery from the nuts under study. Substantial differences in protein profiles, abundance, and IgE-binding intensity with different combinations of pH and ionic strength were found. A significant interaction between pH and ionic strength was observed for pistachio and almond. The optimal buffer system conditions, which maximized the IgE-binding efficiency of allergens and provided satisfactory to superior protein recovery yield and profiles, were carbonate buffer at an ionic strength of I=0.075 for peanut, carbonate buffer at I=0.15 for almond, phosphate buffer at I=0.5 for hazelnut, and borate at I=0.15 for pistachio. The buffer type and its ionic strength could be manipulated to achieve the selective solubility of desired allergens. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Experimental Study on the Velocity and Efficiency Characteristics of a Serial Staged Needle Array-Mesh Type EHD Gas Pump

NASA Astrophysics Data System (ADS)

Qiu, Wei; Xia, Lingzhi; Yang, Lanjun; Zhang, Qiaogen; Xiao, Lei; Chen, Li

2011-12-01

The ionic wind has good application prospects in the fields of air flow control and heat transfer enhancement. The key for successful applications is how to improve the velocity and how to increase the active area of the ionic wind. This paper designed a needle array-mesh type electrohydrodynamic (EHD) gas pump. The use of needle array electrode where corona discharge started simultaneously could enlarge the active area. The velocity of the ionic wind could increase by placing several single-stage ionic wind generators in series appropriately, called as serial staged generator. The maximum average flow velocity of 16.1 m/s and volumetric flow of 303.5 L/min were achieved at the outlet of a 25-stage gas pump and the conversion efficiency was approximately 2.2%.

Generation of Quality Pulses for Control of Qubit/Quantum Memory Spin States: Experimental and Simulation

DTIC Science & Technology

2016-09-01

TECHNICAL REPORT 3046 September 2016 GENERATION OF QUALITY PULSES FOR CONTROL OF QUBIT/QUANTUM MEMORY SPIN STATES: EXPERIMENTAL AND SIMULATION...nuclear spin states of qubits/quantum memory applicable to semiconductor, superconductor, ionic, and superconductor-ionic hybrid technologies. As the...pulse quality and need for development of single pulses with very high quality will impact directly the coherence time of the qubit/ memory , we present

Phytoremediation of Ionic and Methyl Mercury Pollution

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

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems.« less

Phytoremediation of Ionic and Methyl Mercury Pollution

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

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant. To advance this mercury phytoremediation strategy, our planned research focuses on the following Specific Aims: (1) to increase the transport of mercury to aboveground tissue; (2) to identify small mercury binding peptides that enhance hyperaccumulation aboveground; (3) to test the ability of multiple genes acting together to enhance resistance and hyperaccumulation; (4) to construct a simple molecular system for creating male/female sterility, allowing engineered grass, shrub, and tree species to be released indefinitely at contaminated sites; (5) to test the ability of transgenic cottonwood and rice plants to detoxify ionic mercury and prevent methylmercury release from contaminated sediment; and (6) to initiate field testing with transgenic cottonwood and rice for the remediation of methylmercury and ionic mercury. The results of these experiments will enable the phytoremediation of methyl- and ionic mercury by a wide spectrum of deep-rooted, fast-growing plants adapted to diverse environments. We have made significant progress on all six of these specific aims as summarized below.« less

Vaporization of protic ionic liquids derived from organic superbases and short carboxylic acids.

PubMed

Ribeiro, Filipe M S; Lima, Carlos F R A C; Vaz, Inês C M; Rodrigues, Ana S M C; Sapei, Erlin; Melo, André; Silva, Artur M S; Santos, Luís M N B F

2017-06-28

This work presents a comprehensive evaluation of the phase behaviour and cohesive enthalpy of protic ionic liquids (PILs) composed of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) organic superbases with short-chain length (acetic, propionic and butyric) carboxylic acids. Glass transition temperatures, T g , and enthalpies of vaporization, ΔH vap , were measured for six [BH][A] (1 : 1) PILs (B = DBN, DBU; A = MeCOO, EtCOO, nPrCOO), revealing more significant changes upon increasing the number of -CH 2 - groups in the base than in the acid. The magnitude of ΔH vap evidences that liquid PILs have a high proportion of ions, although the results also indicate that in DBN PILs the concentration of neutral species is not negligible. In the gas phase, these PILs exist as a distribution of ion pairs and isolated neutral species, with speciation being dependent on the temperature and pressure conditions - at high temperatures and low pressures the separated neutral species dominate. The higher T g and ΔH vap of the DBU PILs are explained by the stronger basicity of DBU (as supported by NMR and computational calculations), which increases the extent of proton exchange and the ionic character of the corresponding PILs, resulting in stronger intermolecular interactions in condensed phases.

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, A.J.; Barlow, S.E.

1999-08-03

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap`s ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a ``gentle`` environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species. 4 figs.

Ion-exclusion/cation-exchange chromatography with dual detection of the conductivity and spectrophotometry for the simultaneous determination of common inorganic anionic species and cations in river and wastewater.

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Mori, Masanobu; Hasebe, Kiyoshi; Nakagoshi, Nobukazu; Tanaka, Kazuhiko

2011-01-01

Simultaneous determinations of common inorganic anionic species (SO(4)(2-), Cl(-), NO(3)(-), phosphate and silicate) and cations (Na(+), NH(4)(+), K(+), Mg(2+) and Ca(2+)) were conducted using an ion-chromatography system with dual detection of conductivity and spectrophotometry in tandem. The separation of ionic species on a weakly acidic cation-exchange resin was accomplished using a mixture of 100 mM ascorbic acid and 4 mM 18-crown-6 as an acidic eluent (pH 2.6), after which the ions were detected using a conductivity detector. Subsequently, phosphate and silicate were analyzed based on derivatization with molybdate and spectrophotometry at 700 nm. The detection limits at S/N = 3 ranged from 0.11 to 2.9 µM for analyte ionic species. This method was applied to practical river water and wastewater with acceptable criteria for the anion-cation balance and comparisons of the measured and calculated electrical conductivity, demonstrating the usefulness of the present method for water quality monitoring.

Dispersive liquid-liquid microextraction and preconcentration of thallium species in water samples by two ionic liquids applied as ion-pairing reagent and extractant phase.

PubMed

Escudero, Leticia B; Berton, Paula; Martinis, Estefanía M; Olsina, Roberto A; Wuilloud, Rodolfo G

2012-01-15

In the present work, a simple and highly sensitive analytical methodology for determination of Tl(+) and Tl(3+) species, based on the use of modern and non-volatile solvents, such as ionic liquids (ILs), was developed. Initially, Tl(+) was complexed by iodide ion at pH 1 in diluted sulfuric acid solution. Then, tetradecyl(trihexyl)phosphonium chloride ionic liquid (CYPHOS(®) IL 101) was used as ion-pairing reagent and a dispersive liquid-liquid microextraction (DLLME) procedure was developed by dispersing 60 mg of 1-hexyl-3-methylimidazolium hexafluorophosphate [C(6) mim][PF(6)] with 500 μL of ethanol in the aqueous solution. After the microextraction procedure was finished, the final IL phase was solubilized in methanol and directly injected into the graphite furnace of an electrothermal atomic absorption spectrometer (ETAAS). An extraction efficiency of 77% and a sensitivity enhancement factor of 100 were obtained with only 5.00 mL of sample. The limit of detection (LOD) was 3.3 ng L(-1) Tl while the relative standard deviation (RSD) was 5.3% (at 0.4 μg L(-1) Tl and n=10), calculated from the peak height of absorbance signals. The method was finally applied to determine Tl species in tap and river water samples after separation of Tl(3+) species. To the best of our knowledge, this work reports the first application of ILs for Tl extraction and separation in the analytical field. Copyright © 2011 Elsevier B.V. All rights reserved.

The Properties of HPMC:PEO Extended Release Hydrophilic Matrices and their Response to Ionic Environments.

PubMed

Hu, Anran; Chen, Chen; Mantle, Michael D; Wolf, Bettina; Gladden, Lynn F; Rajabi-Siahboomi, Ali; Missaghi, Shahrzad; Mason, Laura; Melia, Colin D

2017-05-01

Investigate the extended release behaviour of compacts containing mixtures of hydrophilic HPMC and PEO in hydrating media of differing ionic strengths. The extended release behaviour of various HPMC:PEO compacts was investigated using dissolution testing, confocal microscopy and magnetic resonance imaging, with respect to polymer ratio and ionic strength of the hydrating media. Increasing HPMC content gave longer extended release times, but a greater sensitivity to high ionic dissolution environments. Increasing PEO content reduced this sensitivity. The addition of PEO to a predominantly HPMC matrix reduced release rate sensitivity to high ionic environments. Confocal microscopy of early gel layer development showed the two polymers appeared to contribute independently to gel layer structure whilst together forming a coherent and effective diffusion barrier. There was some evidence that poorly swollen HPMC particles added a tortuosity barrier to the gel layer in high ionic strength environments, resulting in prolonged extended release. MRI provides unique, non-invasive spatially resolved information from within the HPMC:PEO compacts that furthers our understanding of USP 1 and USP 4 dissolution data. Confocal microscopy and MRI data show that combinations of HPMC and PEO have advantageous extended release properties, in comparison with matrices containing a single polymer.

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf2N ionic liquid.

PubMed

Sandoval, Andrea P; Suárez-Herrera, Marco F; Feliu, Juan M

2015-01-01

Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force microscopy. It was found that the polymer grows faster on Pt(111) than on Pt(110) or Pt(100) and that the redox reactions associated with the PEDOT p-doping process are much more reversible in [EMMIM]Tf2N than in acetonitrile. Finally, the ion exchange and charge carriers' formation during the p-doping reaction of PEDOT were studied using in situ FTIR spectroscopy.

Ultramicroelectrode voltammetry and scanning electrochemical microscopy in room-temperature ionic liquid electrolytes.

PubMed

Walsh, Darren A; Lovelock, Kevin R J; Licence, Peter

2010-11-01

The high viscosity and unusual properties of room temperature ionic liquids (RTILs) present a number of challenges when performing steady-state voltammetry and scanning electrochemical microscopy in RTILs. These include difficulties in recording steady-state currents at ultramicroelectrode surfaces due to low diffusion coefficients of redox species and problems associated with unequal diffusion coefficients of oxidised and reduced species in RTILs. In this tutorial review, we highlight the recent progress in the use of RTILs as electrolytes for ultramicroelectrode voltammetry and SECM. We describe the basic principles of ultramicroelectrode voltammetry and SECM and, using examples from the recent literature, we discuss the conditions that must be met to perform steady-state voltammetry and SECM measurements in RTILs. Finally, we briefly discuss the electrochemical insights that can be obtained from such measurements.

NASA Tech Briefs, March 2011

NASA Technical Reports Server (NTRS)

2011-01-01

Topics covered include: Optimal Tuner Selection for Kalman-Filter-Based Aircraft Engine Performance Estimation; Airborne Radar Interferometric Repeat-Pass Processing; Plug-and-Play Environmental Monitoring Spacecraft Subsystem; Power-Combined GaN Amplifier with 2.28-W Output Power at 87 GHz; Wallops Ship Surveillance System; Source Lines Counter (SLiC) Version 4.0; Guidance, Navigation, and Control Program; Single-Frame Terrain Mapping Software for Robotic Vehicles; Auto Draw from Excel Input Files; Observation Scheduling System; CFDP for Interplanetary Overlay Network; X-Windows Widget for Image Display; Binary-Signal Recovery; Volumetric 3D Display System with Static Screen; MMIC Replacement for Gunn Diode Oscillators; Feature Acquisition with Imbalanced Training Data; Mount Protects Thin-Walled Glass or Ceramic Tubes from Large Thermal and Vibration Loads; Carbon Nanotube-Based Structural Health Monitoring Sensors; Wireless Inductive Power Device Suppresses Blade Vibrations; Safe, Advanced, Adaptable Isolation System Eliminates the Need for Critical Lifts; Anti-Rotation Device Releasable by Insertion of a Tool; A Magnetically Coupled Cryogenic Pump; Single Piezo-Actuator Rotary-Hammering Drill; Fire-Retardant Polymeric Additives; Catalytic Generation of Lift Gases for Balloons; Ionic Liquids to Replace Hydrazine; Variable Emittance Electrochromics Using Ionic Electrolytes and Low Solar Absorptance Coatings; Spacecraft Radiator Freeze Protection Using a Regenerative Heat Exchanger; Multi-Mission Power Analysis Tool; Correction for Self-Heating When Using Thermometers as Heaters in Precision Control Applications; Gravitational Wave Detection with Single-Laser Atom Interferometers; Titanium Alloy Strong Back for IXO Mirror Segments; Improved Ambient Pressure Pyroelectric Ion Source; Multi-Modal Image Registration and Matching for Localization of a Balloon on Titan; Entanglement in Quantum-Classical Hybrid; Algorithm for Autonomous Landing; Quantum-Classical Hybrid for Information Processing; Small-Scale Dissipation in Binary-Species Transitional Mixing Layers; Superpixel-Augmented Endmember Detection for Hyperspectral Images; Coding for Parallel Links to Maximize the Expected Value of Decodable Messages; and Microwave Tissue Soldering for Immediate Wound Closure.

Laser ablation of ceramic Al2O3 at 193 nm and 248 nm: The importance of single-photon ionization processes

NASA Astrophysics Data System (ADS)

Peláez, R. J.; Afonso, C. N.; Bator, M.; Lippert, T.

2013-06-01

The aim of this work is to demonstrate that single-photon photoionization processes make a significant difference in the expansion and temperature of the plasma produced by laser ablation of ceramic Al2O3 in vacuum as well as to show their consequences in the kinetic energy distribution of the species that eventually will impact on the film properties produced by pulsed laser deposition. This work compares results obtained by mass spectrometry and optical spectroscopy on the composition and features of the plasma produced by laser ablation at 193 nm and 248 nm, i.e., photon energies that are, respectively, above and below the ionization potential of Al, and for fluences between threshold for visible plasma and up to ≈2 times higher. The results show that the ionic composition and excitation of the plasma as well as the ion kinetic energies are much higher at 193 nm than at 248 nm and, in the latter case, the population of excited ions is even negligible. The comparison of Maxwell-Boltzmann temperature, electron temperatures, and densities of the plasmas produced with the two laser wavelengths suggests that the expansion of the plasma produced at 248 nm is dominated by a single population. Instead, the one produced at 193 nm is consistent with the existence of two populations of cold and hot species, the latter associated to Al+ ions that travel at the forefront and produced by single photon ionization as well as Al neutrals and double ionized ions produced by electron-ion impact. The results also show that the most energetic Al neutrals in the plasma produced at the two studied wavelengths are in the ground state.

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2012-03-01

particular: “ Molten salts are nothing new, but these were the only ones I ever heard of that were liquid at 25°C. I’ve never found a use for the...Ethylammonium nitrate is generally regarded as the first reported room temperature ionic liquid (RTIL). Since it is a nitrate salt , it certainly...carry the advantages of engineering simplicity associated with the fuel and oxidizer residing in a single tank . However, by itself, ethylammonium

A New Family of Ionic Liquids 1-amino-3-alkyl-1,2,3-Triazolium Nitrates

NASA Technical Reports Server (NTRS)

Drake, Greg; Kaplan, Greg; Hall, Leslie; Hawkins, Tommy; Larue, Joann

2004-01-01

A new class of ionic liquids based upon 1-amino-3-alkyl-1,2,3-triazolium nitrates (alkyl = methyl, ethyl, n-propyl, 2-propeny1, and n-butyl) have been synthesized and characterized by vibrational spectra, multinuclear NMR, elemental analysis, and DSC studies. A single crystal x-ray study was carried out for 1-amino-3-methyl-1,2,3-triazolium nitrate and the details will be presented.

Research@ARL: Materials Modeling at Multiple Scales. Volume 3, Issue 2

DTIC Science & Technology

2014-07-01

possessing high ionic conductivity , low viscosity, and good thermal and electrochemical stability and, importantly, being compatible with electrodes. As... thermal and electrical properties. ARL conducts extensive research in graphene and other 2D materials such as BN, ZnO, and hybrid graphene-polyethylene...contribution at temperatures below 393 K. Thus, below 393 K, Li2EDC essentially acts as a single ion conductor . The isotropic ionic conductivity from MD

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.

The Effect of Lengthening Cation Ether Tails on Ionic Liquid Properties

DOE PAGES

Lall-Ramnarine, S.; Rodriguez, C.; Fernandez, R.; ...

2016-08-30

In order to explore the effect of multiple ether functionalities on ionic liquid properties, a series of ten pyrrolidinium ionic liquids and ten imidazolium ionic liquids bearing ether and alkyl side chains of varying lengths (4 to 10 atoms in length) were prepared for this study. Their physical properties, such as viscosity, conductivity and thermal profile were measured and compared. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase inmore » the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. These results provide significant insight on the choice of starting materials for researchers designing ILs for specific applications.« less

Ultrasound-Assisted Extraction of Carnosic Acid and Rosmarinic Acid Using Ionic Liquid Solution from Rosmarinus officinalis

PubMed Central

Zu, Ge; Zhang, Rongrui; Yang, Lei; Ma, Chunhui; Zu, Yuangang; Wang, Wenjie; Zhao, Chunjian

2012-01-01

Ionic liquid based, ultrasound-assisted extraction was successfully applied to the extraction of phenolcarboxylic acids, carnosic acid and rosmarinic acid, from Rosmarinus officinalis. Eight ionic liquids, with different cations and anions, were investigated in this work and [C8mim]Br was selected as the optimal solvent. Ultrasound extraction parameters, including soaking time, solid–liquid ratio, ultrasound power and time, and the number of extraction cycles, were discussed by single factor experiments and the main influence factors were optimized by response surface methodology. The proposed approach was demonstrated as having higher efficiency, shorter extraction time and as a new alternative for the extraction of carnosic acid and rosmarinic acid from R. officinalis compared with traditional reference extraction methods. Ionic liquids are considered to be green solvents, in the ultrasound-assisted extraction of key chemicals from medicinal plants, and show great potential. PMID:23109836

Ionic liquids as refolding additives: N′-alkyl and N′-(ω-hydroxyalkyl) N-methylimidazolium chlorides

PubMed Central

Lange, Christian; Patil, Ganesh; Rudolph, Rainer

2005-01-01

The purpose of this work was to investigate the influence of a series of N′-alkyl and N′-(ω-hydroxy-alkyl)-N-methylimidazolium chlorides on the renaturation of two model proteins, namely hen egg white lysozyme and the single-chain antibody fragment ScFvOx. All tested ionic liquids acted as refolding enhancers, with varying efficacies and efficiencies. The results of the refolding screening could be interpreted by taking into account the effect of the studied ionic liquids on protein aggregation, together with the systematic variations of their influence on the stability of native proteins in solution. More hydrophobic imidazolium cations carrying longer alkyl chains were increasingly destabilizing, while terminal hydroxylation of the alkyl chain made the salts more compatible with protein stability. The studied ionic liquids can be classified as preferentially bound, slightly to moderately chaotropic cosolvents for proteins. PMID:16195554

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

PubMed Central

Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma; Gogotsi, Yury; Biggs, Mark J.; Salanne, Mathieu; Ségalini, Julie; Simon, Patrice; Kaneko, Katsumi

2017-01-01

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications. PMID:28920938

Sensitive voltammetric determination of chloramphenicol by using single-wall carbon nanotube-gold nanoparticle-ionic liquid composite film modified glassy carbon electrodes.

PubMed

Xiao, Fei; Zhao, Faqiong; Li, Jiangwen; Yan, Rui; Yu, Jingjing; Zeng, Baizhao

2007-07-16

A novel composite film modified glassy carbon electrode has been fabricated and characterized by scanning electron microscope (SEM) and voltammetry. The composite film comprises of single-wall carbon nanotube (SWNT), gold nanoparticle (GNP) and ionic liquid (i.e. 1-octyl-3-methylimidazolium hexafluorophosphate), thus has the characteristics of them. The resulting electrode shows good stability, high accumulation efficiency and strong promotion to electron transfer. On it, chloramphenicol can produce a sensitive cathodic peak at -0.66 V (versus SCE) in pH 7.0 phosphate buffer solutions. Parameters influencing the voltammetric response of chloramphenicol are optimized, which include the composition of the film and the operation conditions. Under the optimized conditions, the peak current is linear to chloramphenicol concentration in the range of 1.0x10(-8)-6.0x10(-6) M, and the detection limit is estimated to be 5.0x10(-9) M after an accumulation for 150 s on open circuit. The electrode is applied to the determination of chloramphenicol in milk samples, and the recoveries for the standards added are 97.0% and 100.3%. In addition, the electrochemical reaction of chloramphenicol and the effect of single-wall carbon nanotube, gold nanoparticle and ionic liquid are discussed.

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

Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

DOEpatents

Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

2002-01-01

The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

NASA Astrophysics Data System (ADS)

Oh, Hyukkeun

Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.

Enzymatically active high-flux selectively gas-permeable membranes

DOEpatents

Jiang, Ying-Bing; Cecchi, Joseph L.; Rempe, Susan; FU, Yaqin; Brinker, C. Jeffrey

2016-01-26

An ultra-thin, catalyzed liquid transport medium-based membrane structure fabricated with a porous supporting substrate may be used for separating an object species such as a carbon dioxide object species. Carbon dioxide flux through this membrane structures may be several orders of magnitude higher than traditional polymer membranes with a high selectivity to carbon dioxide. Other gases such as molecular oxygen, molecular hydrogen, and other species including non-gaseous species, for example ionic materials, may be separated using variations to the membrane discussed.

Ionic Vapor Composition in Critical and Supercritical States of Strongly Interacting Ionic Compounds.

PubMed

Chaban, Vitaly V; Prezhdo, Oleg V

2016-05-12

The critical point, CP (T, P), of the phase diagram quantifies the minimum amount of kinetic energy needed to prevent a substance from existing in a condensed phase. Therefore, the CP is closely related to the properties of the fluid far below the critical temperature. Approaches designed to predict thermophysical properties of a system necessarily aim to provide reliable estimates of the CP. Vice versa, CP estimation is impossible without knowledge of the vapor phase behavior. We report ab initio Born-Oppenheimer molecular dynamics (BOMD) simulations of sodium and potassium chlorides, NaCl and KCl, at and above their expected CPs. We advance the present knowledge regarding the existence of ionic species in the vapor phase by establishing significant percentages of atomic clusters: 29-30% in NaCl and 34-38% in KCl. A neutral pair of counterions is the most abundant cluster in the ionic vapors (ca. 35% of all vaporized ions exist in this form). Unexpectedly, an appreciable fraction of clusters is charged. The ionic vapor composition is determined by the vapor density, rather than the nature of the alkali ion. The previously suggested CPs of NaCl and KCl appear overestimated, based on the present simulations. The reported results offer essential insights into the ionic fluid properties and assist in development of thermodynamic theories. The ab initio BOMD method has been applied to investigate the vapor phase composition of an ionic fluid for the first time.

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.

Interaction between common organic acids and trace nucleation species in the Earth's atmosphere.

PubMed

Xu, Yisheng; Nadykto, Alexey B; Yu, Fangqun; Herb, J; Wang, Wei

2010-01-14

Atmospheric aerosols formed via nucleation in the Earth's atmosphere play an important role in the aerosol radiative forcing associated directly with global climate changes and public health. Although it is well-known that atmospheric aerosol particles contain organic species, the chemical nature of and physicochemical processes behind atmospheric nucleation involving organic species remain unclear. In the present work, the interaction of common organic acids with molecular weights of 122, 116, 134, 88, 136, and 150 (benzoic, maleic, malic, pyruvic, phenylacetic, and tartaric acids) with nucleation precursors and charged trace species has been investigated. We found a moderate strong effect of the organic species on the stability of neutral and charged ionic species. In most cases, the free energies of the mixed H(2)SO(4)-organic acid dimer formation are within 1-1.5 kcal mol(-1) of the (H(2)SO(4))(NH(3)) formation energy. The interaction of the organic acids with trace ionic species is quite strong, and the corresponding free energies far exceed those of the (H(3)O(+))(H(2)SO(4)) and (H(3)O(+))(H(2)SO(4))(2) formation. These considerations lead us to conclude that the aforementioned organic acids may possess a substantial capability of stabilizing both neutral and positively charged prenucleation clusters, and thus, they should be studied further with regard to their involvement in the gas-to-particle conversion in the Earth's atmosphere.

Bridging the gap between ionic liquids and molten salts: group 1 metal salts of the bistriflamide anion in the gas phase.

PubMed

Leal, João P; da Piedade, Manuel E Minas; Canongia Lopes, José N; Tomaszowska, Alina A; Esperança, José M S S; Rebelo, Luís Paulo N; Seddon, Kenneth R

2009-03-19

Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group 1 metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H(+), which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group 1 metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

PubMed Central

Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

2015-01-01

Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials. PMID:26235962

Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating.

PubMed

Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

2015-08-03

Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials.

Long-range electrostatic screening in ionic liquids

PubMed Central

Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

2015-01-01

Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

MURI Center for Materials Chemistry in the Space Environment

DTIC Science & Technology

2006-11-30

ionic species in relevant reaction environments, surface photochemistry expertise, synchrotron-based measurement and irradiation, synthesis of structural...and Ne+ ions with dodecanethiolate and semifluorinated dodecanethiolate self-assembled monolayers (SAM), polyhedral oligomeric silsesquioxane (POSS...POSS/Kapton models as gas phase species, and with alkane thiol self assembled monolayers on gold surfaces, and with liquid squalane. We have also

Thermodynamic evaluation of mass diffusion in ionic mixtures

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

Kagan, Grigory; Tang, Xian-Zhu

2014-02-15

The thermodynamic technique of Landau and Lifshitz originally developed for inter-species diffusion in a binary neutral gas mixture is extended to a quasi-neutral plasma with two ion species. It is shown that, while baro- and electro-diffusion coefficients depend on the choice of the thermodynamic system, prediction for the total diffusive mass flux is invariant.

Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

PubMed

Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

2013-11-19

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

Ionic polymer-metal composite actuators based on triple-layered polyelectrolytes composed of individually functionalized layers.

PubMed

Lee, Jang-Woo; Yoo, Young-Tai; Lee, Jae Yeol

2014-01-22

Ionic polymer-metal composite (IPMC) actuators based on two types of triple-layered Nafion composite membranes were prepared via consecutive solution recasting and electroless plating methods. The triple-layered membranes are composed of a Nafion layer containing an amphiphilic organic molecule (10-camphorsulfonic acid; CSA) in the middle section (for fast and large ion conduction) and two Nafion/modified inorganic composite layers in the outer sections (for large accumulation/retention of mobile ions). For construction of the two types of IPMCs, sulfonated montmorillonite (MMT) and polypyrrole (PPy)-coated alumina fillers were incorporated into the outer layers. Both the triple-layered IPMCs exhibited 42% higher tip displacements at the maximum deflections with a negligible back-relaxation, 50-74% higher blocking forces, and more rapid responses under 3 V dc, compared with conventional single-layered Nafion-IPMCs. Improvements in cyclic displacement under a rectangular voltage input of 3 V at 1 Hz were also made in the triple-layered configurations. Compared with single-layered IPMCs consisting of the identical compositions with the respective outer composite layers, the bending rates and energy efficiencies of both the triple-layered IPMCs were significantly higher, although the blocking forces were a bit lower. These remarkable improvements were attributed to higher capacitances and Young's moduli as well as a more efficient transport of mobile ions and water through the middle layer (Nafion/CSA) and a larger accumulation/retention of the mobile species in the outer functionalized inorganic composite layers. Especially, the triple-layered IPMC with the PPy-modified alumina registered the best actuation performance among all the samples, including a viable actuation even at a low voltage of 1.5 V due to involving efficient redox reactions of PPy with the aid of hygroscopic alumina.

Resolved single-molecule detection of individual species within a mixture of anti-biotin antibodies using an engineered monomeric nanopore.

PubMed

Fahie, Monifa; Chisholm, Christina; Chen, Min

2015-02-24

Oligomeric protein nanopores with rigid structures have been engineered for the purpose of sensing a wide range of analytes including small molecules and biological species such as proteins and DNA. We chose a monomeric β-barrel porin, OmpG, as the platform from which to derive the nanopore sensor. OmpG is decorated with seven flexible loops that move dynamically to create a distinct gating pattern when ionic current passes through the pore. Biotin was chemically tethered to the most flexible one of these loops. The gating characteristic of the loop's movement in and out of the porin was substantially altered by analyte protein binding. The gating characteristics of the pore with bound targets were remarkably sensitive to molecular identity, even providing the ability to distinguish between homologues within an antibody mixture. A total of five gating parameters were analyzed for each analyte to create a unique fingerprint for each biotin-binding protein. Our exploitation of gating noise as a molecular identifier may allow more sophisticated sensor design, while OmpG's monomeric structure greatly simplifies nanopore production.

Ionic-liquid-impregnated resin for the microwave-assisted solid-liquid extraction of triazine herbicides in honey.

PubMed

Wu, Lijie; Song, Ying; Hu, Mingzhu; Yu, Cui; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

2015-09-01

Microwave-assisted ionic-liquid-impregnated resin solid-liquid extraction was developed for the extraction of triazine herbicides, including cyanazine, metribuzin, desmetryn, secbumeton, terbumeton, terbuthylazine, dimethametryn, and dipropetryn in honey samples. The ionic-liquid-impregnated resin was prepared by immobilizing 1-hexyl-3-methylimidazolium hexafluorophosphate in the microspores of resin. The resin was used as the extraction adsorbent. The extraction and enrichment of analytes were performed in a single step. The extraction time can be shortened greatly with the help of microwave. The effects of experimental parameters including type of resin, type of ionic liquid, mass ratio of resin to ionic liquid, extraction time, amount of the impregnated resin, extraction temperature, salt concentration, and desorption conditions on the extraction efficiency, were investigated. A Box-Behnken design was applied to the selection of the experimental parameters. The recoveries were in the range of 80.1 to 103.4% and the relative standard deviations were lower than 6.8%. The present method was applied to the analysis of honey samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of a Protic Ionic Liquid on the Reaction Pathway during Non-Aqueous Sol–Gel Synthesis of Silica: A Raman Spectroscopic Investigation

PubMed Central

Martinelli, Anna

2014-01-01

The reaction pathway during the formation of silica via a two-component “non-aqueou” sol-gel synthesis is studied by in situ time-resolved Raman spectroscopy. This synthetic route is followed with and without the addition of the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide (C2HImTFSI) in order to investigate its effect on the reaction pathway. We demonstrate that Raman spectroscopy is suitable to discriminate between different silica intermediates, which are produced and consumed at different rates with respect to the point of gelation. We find that half-way to gelation monomers and shorter chains are the most abundant silica species, while the formation of silica rings strongly correlates to the sol-to-gel transition. Thus, curling up of linear chains is here proposed as a plausible mechanism for the formation of small rings. These in turn act as nucleation sites for the condensation of larger rings and thus the formation of the open and polymeric silica network. We find that the protic ionic liquid does not change the reaction pathway per se, but accelerates the cyclization process, intermediated by the faster inclusion of monomeric species. PMID:24743891

A microdot multilayer oxide device: let us tune the strain-ionic transport interaction.

PubMed

Schweiger, Sebastian; Kubicek, Markus; Messerschmitt, Felix; Murer, Christoph; Rupp, Jennifer L M

2014-05-27

In this paper, we present a strategy to use interfacial strain in multilayer heterostructures to tune their resistive response and ionic transport as active component in an oxide-based multilayer microdot device on chip. For this, fabrication of strained multilayer microdot devices with sideways attached electrodes is reported with the material system Gd0.1Ce0.9O(2-δ)/Er2O3. The fast ionic conducting Gd0.1Ce0.9O(2-δ) single layers are altered in lattice strain by the electrically insulating erbia phases of a microdot. The strain activated volume of the Gd0.1Ce0.9O(2-δ) is investigated by changing the number of individual layers from 1 to 60 while keeping the microdot at a constant thickness; i.e., the proportion of strained volume was systematically varied. Electrical measurements showed that the activation energy of the devices could be altered by Δ0.31 eV by changing the compressive strain of a microdot ceria-based phase by more than 1.16%. The electrical conductivity data is analyzed and interpreted with a strain volume model and defect thermodynamics. Additionally, an equivalent circuit model is presented for sideways contacted multilayer microdots. We give a proof-of-concept for microdot contacting to capture real strain-ionic transport effects and reveal that for classic top-electrode contacting the effect is nil, highlighting the need for sideways electric contacting on a nanoscopic scale. The near order ionic transport interaction is supported by Raman spectroscopy measurements. These were conducted and analyzed together with fully relaxed single thin film samples. Strain states are described relative to the strain activated volumes of Gd0.1Ce0.9O(2-δ) in the microdot multilayer. These findings reveal that strain engineering in microfabricated devices allows altering the ionic conduction over a wide range beyond classic doping strategies for single films. The reported fabrication route and concept of strained multilayer microdots is a promising path for applying strained multilayer oxides as active new building blocks relevant for a broad range of microelectrochemical devices, e.g., resistive switching memory prototypes, resistive or electrochemical sensors, or as active catalytic solid state surface components for microfuel cells or all-solid-state batteries.

Competitive counterion complexation allows the true host : guest binding constants from a single titration by ionic receptors.

PubMed

Pessêgo, Márcia; Basílio, Nuno; Muñiz, M Carmen; García-Río, Luis

2016-07-06

Counterion competitive complexation is a background process currently ignored by using ionic hosts. Consequently, guest binding constants are strongly affected by the design of the titration experiments in such a way that the results are dependent on the guest concentration and on the presence of added salts, usually buffers. In the present manuscript we show that these experimental difficulties can be overcome by just considering the counterion competitive complexation. Moreover a single titration allows us to obtain not only the true binding constants but also the stoichiometry of the complex showing the formation of 1 : 1 : 1 (host : guest : counterion) complexes. The detection of high stoichiometry complexes is not restricted to a single titration experiment but also to a displacement assay where both competitive and competitive-cooperative complexation models are taken into consideration.

Grotthuss Transport of Iodide in EMIM/I3 Ionic Crystal.

PubMed

McDaniel, Jesse G; Yethiraj, Arun

2018-01-11

Highly ionic environments can mediate unusual chemical reactions that would otherwise be considered impossible based on chemical intuition. For example, the formation of a chemical bond between two iodide anions to form a divalent polyiodide anion is seemingly prohibited due to Coulombic repulsion. Using ab initio molecular dynamics simulations, we show that in the 1-ethyl-3-methylimidazolium (EMIM)/I 3 ionic crystal, the reactive formation of divalent and even trivalent polyiodide anions occurs with extremely small energetic barriers, due to the electrostatic field of the ionic lattice. A practical consequence of this anomalous reactivity is that iodide anions are efficiently transported within the crystal through a "Grotthuss-exchange" mechanism involving bond-breaking and forming events. We characterize two distinct transport pathways, involving both I 4 2- and I 7 3- intermediates, with fast transport of iodide resulting from the release of an I - anion on the opposite side of the intermediate species from the initial bond formation. The ordered cation arrangement in the crystal provides the necessary electrostatic screening for close approach of anions, suggesting a new counterintuitive approach to obtain high ionic conductivity. This new design principle could be used to develop better solid-state electrolytes for batteries, fuel cells, and supercapacitors.

Surface Adsorption in Nonpolarizable Atomic Models.

PubMed

Whitmer, Jonathan K; Joshi, Abhijeet A; Carlton, Rebecca J; Abbott, Nicholas L; de Pablo, Juan J

2014-12-09

Many ionic solutions exhibit species-dependent properties, including surface tension and the salting-out of proteins. These effects may be loosely quantified in terms of the Hofmeister series, first identified in the context of protein solubility. Here, our interest is to develop atomistic models capable of capturing Hofmeister effects rigorously. Importantly, we aim to capture this dependence in computationally cheap "hard" ionic models, which do not exhibit dynamic polarization. To do this, we have performed an investigation detailing the effects of the water model on these properties. Though incredibly important, the role of water models in simulation of ionic solutions and biological systems is essentially unexplored. We quantify this via the ion-dependent surface attraction of the halide series (Cl, Br, I) and, in so doing, determine the relative importance of various hypothesized contributions to ionic surface free energies. Importantly, we demonstrate surface adsorption can result in hard ionic models combined with a thermodynamically accurate representation of the water molecule (TIP4Q). The effect observed in simulations of iodide is commensurate with previous calculations of the surface potential of mean force in rigid molecular dynamics and polarizable density-functional models. Our calculations are direct simulation evidence of the subtle but sensitive role of water thermodynamics in atomistic simulations.

Electrophoretic mobilities of erythrocytes in various buffers

NASA Technical Reports Server (NTRS)

Plank, L. D.; Kunze, M. E.; Todd, P. W.

1985-01-01

The calibration of space flight equipment depends on a source of standard test particles, this test particle of choice is the fixed erythrocyte. Erythrocytes from different species have different electrophoretic mobilities. Electrophoretic mobility depends upon zeta potential, which, in turn depends upon ionic strength. Zeta potential decreases with increasing ionic strength, so cells have high electrophoretic mobility in space electrophoresis buffers than in typical physiological buffers. The electrophoretic mobilities of fixed human, rat, and rabbit erythrocytes in 0.145 M salt and buffers of varying ionic strength, temperature, and composition, to assess the effects of some of the unique combinations used in space buffers were characterized. Several effects were assessed: glycerol or DMSO (dimethylsulfoxide) were considered for use as cryoprotectants. The effect of these substances on erythrocyte electrophoretic mobility was examined. The choice of buffer depended upon cell mobility. Primary experiments with kidney cells established the choice of buffer and cryoprotectant. A nonstandard temperature of EPM in the suitable buffer was determined. A loss of ionic strength control occurs in the course of preparing columns for flight, the effects of small increases in ionic strength over the expected low values need to be evaluated.

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.

Modelling the influence of ionic and fluid transport on rebars corrosion in unsaturated cement systems

NASA Astrophysics Data System (ADS)

Dridi, W.; Dangla, P.; Foct, F.; Petre-Lazar, I.

2006-11-01

This paper deals with numerical modelling of rebar corrosion kinetics in unsaturated concrete structures. The corrosion kinetics is investigated in terms of mechanistic coupling between reaction rates at the steel surface and the ionic transport processes in the concrete pore system. The ionic and mass transport model consists of time-dependent equations for the concentration of dissolved species, the liquid pressure and the electrical potential. The complete set of nonlinear equations is solved using the finite-volume method. The nonlinear boundary conditions dealing with corrosion are introduced at the steel-concrete interface where they are implicitly coupled with the mass transport model in the concrete structure. Both the case of free corrosion and potentiostatic polarisation are discussed in a one dimensional model.

Experimental and Theoretical Study on Supramolecular Ionic Liquid (IL)-Asphaltene Complex Interactions and Their Effects on the Flow Properties of Heavy Crude Oils.

PubMed

Hernández-Bravo, R; Miranda, A D; Martínez-Magadán, J-M; Domínguez, J M

2018-04-19

A combined study for understanding the molecular interactions of asphaltenes with molecular species such as ionic liquids (ILs) comprised experimental measurements and computational numerical simulation calculations, using density-functional theory (DFT) with dispersion corrections, molecular dynamics (MD) calculations, and experimental rheological characterization of the heavy crude oils (HCOs), before and after doping with ILs, respectively. The main results show that ILs influence the asphaltenic dimer association by forming supramolecular complexes that modify the properties of crude oils such as viscosity and interfacial tension. The IL-cation and asphaltene-π ligand molecular interactions seem to dominate the interactions between ionic liquids and asphaltenes, where ILs' high aromaticity index induces a strong interaction with the aromatic hard core of asphaltenes.

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

PubMed

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Combining piracetam and lithium salts: ionic co-crystals and co-drugs?

PubMed

Braga, Dario; Grepioni, Fabrizia; Maini, Lucia; Capucci, Davide; Nanna, Saverio; Wouters, Johan; Aerts, Luc; Quéré, Luc

2012-08-25

Mechanochemical reaction of solid piracetam with the inorganic salts LiCl and LiBr yields ionic co-crystals which are also co-drugs, characterized by markedly different thermal properties with respect to pure components, also depending on the method for preparation and/or conditions of measurements; single crystal and powder X-ray diffraction at variable temperatures, DSC, TGA, hot stage microscopy (HSM) and intrinsic dissolution rate have been used to fully characterize the solid products.

Graphene Visualizes the Ion Distribution on Air-Cleaved Mica.

PubMed

Bampoulis, Pantelis; Sotthewes, Kai; Siekman, Martin H; Zandvliet, Harold J W; Poelsema, Bene

2017-03-06

The distribution of potassium (K + ) ions on air-cleaved mica is important in many interfacial phenomena such as crystal growth, self-assembly and charge transfer on mica. However, due to experimental limitations to nondestructively probe single ions and ionic domains, their exact lateral organization is yet unknown. We show, by the use of graphene as an ultra-thin protective coating and scanning probe microscopies, that single potassium ions form ordered structures that are covered by an ice layer. The K + ions prefer to minimize the number of nearest neighbour K + ions by forming row-like structures as well as small domains. This trend is a result of repulsive ionic forces between adjacent ions, weakened due to screening by the surrounding water molecules. Using high resolution conductive atomic force microscopy maps, the local conductance of the graphene is measured, revealing a direct correlation between the K + distribution and the structure of the ice layer. Our results shed light on the local distribution of ions on the air-cleaved mica, solving a long-standing enigma. They also provide a detailed understanding of charge transfer from the ionic domains towards graphene.

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf2N ionic liquid

PubMed Central

Sandoval, Andrea P; Suárez-Herrera, Marco F

2015-01-01

Summary Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force microscopy. It was found that the polymer grows faster on Pt(111) than on Pt(110) or Pt(100) and that the redox reactions associated with the PEDOT p-doping process are much more reversible in [EMMIM]Tf2N than in acetonitrile. Finally, the ion exchange and charge carriers’ formation during the p-doping reaction of PEDOT were studied using in situ FTIR spectroscopy. PMID:25815089

Single DNA molecule detection using nanopipettes and nanoparticles.

PubMed

Karhanek, Miloslav; Kemp, Jennifer T; Pourmand, Nader; Davis, Ronald W; Webb, Chris D

2005-02-01

Single DNA molecules labeled with nanoparticles can be detected by blockades of ionic current as they are translocated through a nanopipette tip formed by a pulled glass capillary. The nanopipette detection technique can provide not only tools for detection and identification of single DNA and protein molecules but also deeper insight and understanding of stochastic interactions of various biomolecules with their environment.

The development of a site-specific water-quality standard for copper

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

Sinclair, R.M.

This dissertation proposes to determine, for one toxic chemical, copper, if the Federal water quality standard and the state interpretation of that standard are appropriate for the Duck River, some 50 miles south of Nashville, Tennessee. This involved conducting toxicity tests in Duck River water, and the use of the computer metal speciation program MINTEQA1 to predict instream impact. The speciation model chosen for the determination of chemical equilibria in this study was MINTEQA1. To test the validity of the MINTEQA1 speciation model, water chemistry from the Duck River was entered into the model. At the typical site pH ofmore » 7.8, 55.7% of the copper is bound as Cu(OH){sub 2}, 29.8% is bound as copper humate, and 12.7% is found as CuCO{sub 3}. Of extreme importance to the toxicity of copper in the site water is the complete absence of the most toxic species, ionic copper. The test species were the brook silversides minnow (Labidesthes sicculus), mosquitofish (Gambusia affinis), caddisfly larvae (Cheumatopsyche sp.), fathead minnow (Pimephales promelas), geniculate river snail (Lithasia geniculata), sunfish (Lepomis sp.), and the amphipod (Hyalella azeca). The test concentrations were confirmed by atomic absorption spectroscopy on selected concentrations. The caddisfly larvae was the single most tolerant species observed during this study, while the amphipod and snail were the two most sensitive species tested.« less

Effect of defocusing on laser ablation plume observed by laser-induced fluorescence imaging spectroscopy

NASA Astrophysics Data System (ADS)

Oba, Masaki; Miyabe, Masabumi; Akaoka, Katsuaki; Wakaida, Ikuo

2016-02-01

We used laser-induced fluorescence imaging with a varying beam focal point to observe ablation plumes from metal and oxide samples of gadolinium. The plumes expand vertically when the focal point is far from the sample surface. In contrast, the plume becomes hemispherical when the focal point is on the sample surface. In addition, the internal plume structure and the composition of the ablated atomic and ionic particles also vary significantly. The fluorescence intensity of a plume from a metal sample is greater than that from an oxide sample, which suggests that the number of monatomic species produced in each plume differs. For both the metal and oxide samples, the most intense fluorescence from atomic (ionic) species is observed with the beam focal point at 3-4 mm (2 mm) from the sample surface.

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.

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects.

PubMed

Pastor, María Jesús; Cuerva, Cristián; Campo, José A; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-05-12

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO R(n)pyH ]⁺ and BF₄ - , ReO₄ - , NO₃ - , CF₃SO₃ - , CuCl₄ 2- counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO R(12)pyH ][ReO₄] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl₄ 2- salts exhibit the best LC properties followed by the ReO₄ - ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO₄ - , and CuCl₄ 2- families, and for the solid phase in one of the non-mesomorphic Cl - salts. The highest ionic conductivity was found for the smectic mesophase of the ReO₄ - containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Frequency-Stable Ionic-Type Hybrid Gate Dielectrics for High Mobility Solution-Processed Metal-Oxide Thin-Film Transistors

PubMed Central

Heo, Jae Sang; Choi, Seungbeom; Jo, Jeong-Wan; Kang, Jingu; Park, Ho-Hyun; Kim, Yong-Hoon; Park, Sung Kyu

2017-01-01

In this paper, we demonstrate high mobility solution-processed metal-oxide thin-film transistors (TFTs) by using a high-frequency-stable ionic-type hybrid gate dielectric (HGD). The HGD gate dielectric, a blend of sol-gel aluminum oxide (AlOx) and poly(4-vinylphenol) (PVP), exhibited high dielectric constant (ε~8.15) and high-frequency-stable characteristics (1 MHz). Using the ionic-type HGD as a gate dielectric layer, an minimal electron-double-layer (EDL) can be formed at the gate dielectric/InOx interface, enhancing the field-effect mobility of the TFTs. Particularly, using the ionic-type HGD gate dielectrics annealed at 350 °C, InOx TFTs having an average field-effect mobility of 16.1 cm2/Vs were achieved (maximum mobility of 24 cm2/Vs). Furthermore, the ionic-type HGD gate dielectrics can be processed at a low temperature of 150 °C, which may enable their applications in low-thermal-budget plastic and elastomeric substrates. In addition, we systematically studied the operational stability of the InOx TFTs using the HGD gate dielectric, and it was observed that the HGD gate dielectric effectively suppressed the negative threshold voltage shift during the negative-illumination-bias stress possibly owing to the recombination of hole carriers injected in the gate dielectric with the negatively charged ionic species in the HGD gate dielectric. PMID:28772972

Introducing catalyst in alkaline membrane for improved performance direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Qin, Haiying; Lin, Longxia; Chu, Wen; Jiang, Wei; He, Yan; Shi, Qiao; Deng, Yonghong; Ji, Zhenguo; Liu, Jiabin; Tao, Shanwen

2018-01-01

A catalytic material is introduced into the polymer matrix to prepare a novel polymeric alkaline electrolyte membrane (AEM) which simultaneously increases ionic conductivity, reduces the fuel cross-over. In this work, the hydroxide anion exchange membrane is mainly composed of poly(vinylalcohol) and alkaline exchange resin. CoCl2 is added into the poly(vinylalcohol) and alkaline exchange resin gel before casting the membrane to introduce catalytic materials. CoCl2 is converted into CoOOH after the reaction with KOH solution. The crystallinity of the polymer matrix decreases and the ionic conductivity of the composite membrane is notably improved by the introduction of Co-species. A direct borohydride fuel cell using the composite membrane exhibits an open circuit voltage of 1.11 V at 30 °C, which is notably higher than that of cells using other AEMs. The cell using the composite membrane achieves a maximum power density of 283 mW cm-2 at 60 °C while the cell using the membrane without Co-species only reaches 117 mW cm-2 at the same conditions. The outstanding performance of the cell using the composite membrane benefits from impregnation of the catalytic Co-species in the membrane, which not only increases the ionic conductivity but also reduces electrode polarization thus improves the fuel cell performance. This work provides a new approach to develop high-performance fuel cells through adding catalysts in the electrolyte membrane.

Effect of organic salt doping on the performance of single layer bulk heterojunction organic solar cell

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

Yap, C.C.; Yahaya, M.; Salleh, M.M.

2011-01-15

The effect of organic salt, tetrabutylammonium hexafluorophosphate (TBAPF{sub 6}) doping on the performance of single layer bulk heterojunction organic solar cell with ITO/MEHPPV:PCBM/Al structure was investigated where indium tin oxide (ITO) was used as anode, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV) as donor, (6,6)-phenyl-C61 butyric acid methyl ester (PCBM) as acceptor and aluminium (Al) as cathode. In contrast to the undoped device, the electric field-treated device doped with TBAPF{sub 6} exhibited better solar cell performance under illumination with a halogen projector lamp at 100 mW/cm{sup 2}. The short circuit current density and the open circuit voltage of the doped device increased from 0.54 {mu}A/cm{supmore » 2} to 6.41 {mu}A/cm{sup 2} and from 0.24 V to 0.50 V, respectively as compared to those of the undoped device. The significant improvement was attributed to the increase of built-in electric field caused by accumulation of ionic species at the active layer/electrode interfaces. (author)« less

Highly Accurate Classification of Watson-Crick Basepairs on Termini of Single DNA Molecules

PubMed Central

Winters-Hilt, Stephen; Vercoutere, Wenonah; DeGuzman, Veronica S.; Deamer, David; Akeson, Mark; Haussler, David

2003-01-01

We introduce a computational method for classification of individual DNA molecules measured by an α-hemolysin channel detector. We show classification with better than 99% accuracy for DNA hairpin molecules that differ only in their terminal Watson-Crick basepairs. Signal classification was done in silico to establish performance metrics (i.e., where train and test data were of known type, via single-species data files). It was then performed in solution to assay real mixtures of DNA hairpins. Hidden Markov Models (HMMs) were used with Expectation/Maximization for denoising and for associating a feature vector with the ionic current blockade of the DNA molecule. Support Vector Machines (SVMs) were used as discriminators, and were the focus of off-line training. A multiclass SVM architecture was designed to place less discriminatory load on weaker discriminators, and novel SVM kernels were used to boost discrimination strength. The tuning on HMMs and SVMs enabled biophysical analysis of the captured molecule states and state transitions; structure revealed in the biophysical analysis was used for better feature selection. PMID:12547778

Factors and sources influencing ionic composition of atmospheric condensate during winter season in lower troposphere over Delhi, India.

PubMed

Kumar, Pawan; Yadav, Sudesh

2013-03-01

Atmospheric condensate (AC) and rainwater samples were collected during 2010-2011 winter season from Delhi and characterized for major cations and anions. The observed order of abundance of cations and anions in AC samples was NH (4) (+)  > Ca(2+) > Na(+) > K(+) > Mg(2+) and HCO (3) (-)  > SO (4) (2-)  > Cl(-) > NO (2) (-)  > NO (3) (-)  > F(-), respectively. All samples were alkaline in nature and Σ (cation)/Σ (anion) ratio was found to be close to one. NH (4) (+) emissions followed by Ca(2+) and Mg(2+) were largely responsible for neutralization of acidity caused by high NO( x ) and SO(2) emissions from vehicles and thermal power plants in the region. Interestingly, AC samples show low nitrate content compared with its precursor nitrite, which is commonly reversed in case of rainwater. It could be due to (1) slow light-mediated oxidation of HONO; (2) larger emission of NO(2) and temperature inversion conditions entrapping them; and (3) formation and dissociation of ammonium nitrite, which seems to be possible as both carry close correlation in our data set. Principal component analysis indicated three factors (marine mixed with biomass burning, anthropogenic and terrestrial, and carbonates) for all ionic species. Significantly higher sulfate/nitrate ratio indicates greater anthropogenic contributions in AC samples compared with rainwater. Compared with rainwater, AC samples show higher abundance of all ionic species except SO(4), NO(3), and Ca suggesting inclusion of these ions by wash out process during rain events. Ionic composition and related variations in AC and rainwater samples indicate that two represent different processes in time and space coordinates. AC represents the near-surface interaction whereas rainwater chemistry is indicative of regional patterns. AC could be a suitable way to understand atmospheric water interactions with gas and solid particle species in the lower atmosphere.

Fitting membrane resistance along with action potential shape in cardiac myocytes improves convergence: application of a multi-objective parallel genetic algorithm.

PubMed

Kaur, Jaspreet; Nygren, Anders; Vigmond, Edward J

2014-01-01

Fitting parameter sets of non-linear equations in cardiac single cell ionic models to reproduce experimental behavior is a time consuming process. The standard procedure is to adjust maximum channel conductances in ionic models to reproduce action potentials (APs) recorded in isolated cells. However, vastly different sets of parameters can produce similar APs. Furthermore, even with an excellent AP match in case of single cell, tissue behaviour may be very different. We hypothesize that this uncertainty can be reduced by additionally fitting membrane resistance (Rm). To investigate the importance of Rm, we developed a genetic algorithm approach which incorporated Rm data calculated at a few points in the cycle, in addition to AP morphology. Performance was compared to a genetic algorithm using only AP morphology data. The optimal parameter sets and goodness of fit as computed by the different methods were compared. First, we fit an ionic model to itself, starting from a random parameter set. Next, we fit the AP of one ionic model to that of another. Finally, we fit an ionic model to experimentally recorded rabbit action potentials. Adding the extra objective (Rm, at a few voltages) to the AP fit, lead to much better convergence. Typically, a smaller MSE (mean square error, defined as the average of the squared error between the target AP and AP that is to be fitted) was achieved in one fifth of the number of generations compared to using only AP data. Importantly, the variability in fit parameters was also greatly reduced, with many parameters showing an order of magnitude decrease in variability. Adding Rm to the objective function improves the robustness of fitting, better preserving tissue level behavior, and should be incorporated.

Computation of methodology-independent single-ion solvation properties from molecular simulations. IV. Optimized Lennard-Jones interaction parameter sets for the alkali and halide ions in water

NASA Astrophysics Data System (ADS)

Reif, Maria M.; Hünenberger, Philippe H.

2011-04-01

The raw single-ion solvation free energies computed from atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [M. A. Kastenholz and P. H. Hünenberger, J. Chem. Phys. 124, 224501 (2006), 10.1529/biophysj.106.083667; M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144103 (2010)], the application of appropriate correction terms permits to obtain methodology-independent results. The corrected values are then exclusively characteristic of the underlying molecular model including in particular the ion-solvent van der Waals interaction parameters, determining the effective ion size and the magnitude of its dispersion interactions. In the present study, the comparison of calculated (corrected) hydration free energies with experimental data (along with the consideration of ionic polarizabilities) is used to calibrate new sets of ion-solvent van der Waals (Lennard-Jones) interaction parameters for the alkali (Li+, Na+, K+, Rb+, Cs+) and halide (F-, Cl-, Br-, I-) ions along with either the SPC or the SPC/E water models. The experimental dataset is defined by conventional single-ion hydration free energies [Tissandier et al., J. Phys. Chem. A 102, 7787 (1998), 10.1021/jp982638r; Fawcett, J. Phys. Chem. B 103, 11181] along with three plausible choices for the (experimentally elusive) value of the absolute (intrinsic) hydration free energy of the proton, namely, Δ G_hyd^{ominus }[H+] = -1100, -1075 or -1050 kJ mol-1, resulting in three sets L, M, and H for the SPC water model and three sets LE, ME, and HE for the SPC/E water model (alternative sets can easily be interpolated to intermediate Δ G_hyd^{ominus }[H+] values). The residual sensitivity of the calculated (corrected) hydration free energies on the volume-pressure boundary conditions and on the effective ionic radius entering into the calculation of the correction terms is also evaluated and found to be very limited. Ultimately, it is expected that comparison with other experimental ionic properties (e.g., derivative single-ion solvation properties, as well as data concerning ionic crystals, melts, solutions at finite concentrations, or nonaqueous solutions) will permit to validate one specific set and thus, the associated Δ G_hyd^{ominus }[H+] value (atomistic consistency assumption). Preliminary results (first-peak positions in the ion-water radial distribution functions, partial molar volumes of ionic salts in water, and structural properties of ionic crystals) support a value of Δ G_hyd^{ominus }[H+] close to -1100 kJ.mol-1.

Surfactant Behavior of Sodium Dodecylsulfate in Deep Eutectic Solvent Choline Chloride/Urea.

PubMed

Arnold, T; Jackson, A J; Sanchez-Fernandez, A; Magnone, D; Terry, A E; Edler, K J

2015-12-01

Deep eutectic solvents (DES) resemble ionic liquids but are formed from an ionic mixture instead of being a single ionic compound. Here we present some results that demonstrate that surfactant sodium dodecyl sulfate (SDS) remains surface-active and shows self-assembly phenomena in the most commonly studied DES, choline chloride/urea. X-ray reflectivity (XRR) and small angle neutron scattering (SANS) suggest that the behavior is significantly different from that in water. Our SANS data supports our determination of the critical micelle concentration using surface-tension measurements and suggests that the micelles formed in DES do not have the same shape and size as those seen in water. Reflectivity measurements have also demonstrated that the surfactants remain surface-active below this concentration.

Asian Influence Over the Western North Pacific during the Fall Season: Inferences from Lead 210, Soluble Ionic Species and Ozone

NASA Technical Reports Server (NTRS)

Dibb, J. E.; Talbot, R. W.; Klemm, K. I.; Gregory, G. L.; Singh, H. B.; Bradshaw, J. D.; Sandholm, S. T.

1996-01-01

Aerosol samples collected over the western Pacific during the NASA/Global Tropospheric Experiment Pacific Exploratory Mission (PEM-West A) expedition (September - October 1991) revealed mean Pb-210 concentrations in the free troposphere in the 5-10 fCi m(exp -3) STP range. Most soluble ionic aerosol-associated species were near detection limits [much less than 40 parts per trillion by volume (pptv)] in these same samples. The altitude distribution of O3 near Asia closely resembled that of Pb-210, while no relationship was found between the concentrations of O3 and Be-7. Free tropospheric air over the western Pacific was depleted in soluble aerosol-associated species but enriched in Pb-210 and O3, indicative of deep wet convection over the Asian continent. The influence of Asian air on the composition of the free troposphere over the western Pacific was evident on most of the PEM-West A flights. However, evidence of continental influence was largely restricted to those species that are relatively insoluble (or have insoluble precursors), hence escape scavenging during vertical transport from the boundary layer into the free troposphere by wet convective activity.

Solutions to a reduced Poisson–Nernst–Planck system and determination of reaction rates

PubMed Central

Li, Bo; Lu, Benzhuo; Wang, Zhongming; McCammon, J. Andrew

2010-01-01

We study a reduced Poisson–Nernst–Planck (PNP) system for a charged spherical solute immersed in a solvent with multiple ionic or molecular species that are electrostatically neutralized in the far field. Some of these species are assumed to be in equilibrium. The concentrations of such species are described by the Boltzmann distributions that are further linearized. Others are assumed to be reactive, meaning that their concentrations vanish when in contact with the charged solute. We present both semi-analytical solutions and numerical iterative solutions to the underlying reduced PNP system, and calculate the reaction rate for the reactive species. We give a rigorous analysis on the convergence of our simple iteration algorithm. Our numerical results show the strong dependence of the reaction rates of the reactive species on the magnitude of its far field concentration as well as on the ionic strength of all the chemical species. We also find non-monotonicity of electrostatic potential in certain parameter regimes. The results for the reactive system and those for the non-reactive system are compared to show the significant differences between the two cases. Our approach provides a means of solving a PNP system which in general does not have a closed-form solution even with a special geometrical symmetry. Our findings can also be used to test other numerical methods in large-scale computational modeling of electro-diffusion in biological systems. PMID:20228879

Ice nucleation in nature: supercooling point (SCP) measurements and the role of heterogeneous nucleation.

PubMed

Wilson, P W; Heneghan, A F; Haymet, A D J

2003-02-01

In biological systems, nucleation of ice from a supercooled aqueous solution is a stochastic process and always heterogeneous. The average time any solution may remain supercooled is determined only by the degree of supercooling and heterogeneous nucleation sites it encounters. Here we summarize the many and varied definitions of the so-called "supercooling point," also called the "temperature of crystallization" and the "nucleation temperature," and exhibit the natural, inherent width associated with this quantity. We describe a new method for accurate determination of the supercooling point, which takes into account the inherent statistical fluctuations of the value. We show further that many measurements on a single unchanging sample are required to make a statistically valid measure of the supercooling point. This raises an interesting difference in circumstances where such repeat measurements are inconvenient, or impossible, for example for live organism experiments. We also discuss the effect of solutes on this temperature of nucleation. Existing data appear to show that various solute species decrease the nucleation temperature somewhat more than the equivalent melting point depression. For non-ionic solutes the species appears not to be a significant factor whereas for ions the species does affect the level of decrease of the nucleation temperature.

An analytic expression for the sheath criterion in magnetized plasmas with multi-charged ion species

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

Hatami, M. M., E-mail: m-hatami@kntu.ac.ir

2015-04-15

The generalized Bohm criterion in magnetized multi-component plasmas consisting of multi-charged positive and negative ion species and electrons is analytically investigated by using the hydrodynamic model. It is assumed that the electrons and negative ion density distributions are the Boltzmann distribution with different temperatures and the positive ions enter into the sheath region obliquely. Our results show that the positive and negative ion temperatures, the orientation of the applied magnetic field and the charge number of positive and negative ions strongly affect the Bohm criterion in these multi-component plasmas. To determine the validity of our derived generalized Bohm criterion, itmore » reduced to some familiar physical condition and it is shown that monotonically reduction of the positive ion density distribution leading to the sheath formation occurs only when entrance velocity of ion into the sheath satisfies the obtained Bohm criterion. Also, as a practical application of the obtained Bohm criterion, effects of the ionic temperature and concentration as well as magnetic field on the behavior of the charged particle density distributions and so the sheath thickness of a magnetized plasma consisting of electrons and singly charged positive and negative ion species are studied numerically.« less

Dissecting the steps of CO2 reduction: 2. The interaction of CO and CO2 with Pd/γ-Al2O3: an in situ FTIR study

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

Szanyi, Janos; Kwak, Ja Hun

2014-08-07

Alumina supported Pd catalysts with metal loadings of 0.5, 2.5 and 10 wt% were investigated by in situ FTIR spectroscopy in order to understand the nature of adsorbed species formed during their exposure to CO2 and CO. Exposing the annealed samples to CO2 at 295 K resulted in the formation of alumina support-bound surface species only: linear adsorbed CO2, bidentate carbonates and bicarbonates. Room temperature exposure of all three samples to CO produced IR features characteristic of both ionic and metallic Pd, as well as bands we observed upon CO2 adsorption (alumina support-bound species). Low temperature (100 K) adsorption ofmore » CO on the three samples provided information about the state of Pd after oxidation and reduction. Oxidized samples contained exclusively ionic Pd, while mostly metallic Pd was present in the reduced samples. Subsequent annealing of the CO-saturated samples revealed the facile (low temperature) reduction of PdOx species by adsorbed CO. This process was evidenced by the variations in IR bands characteristic of ionic and metallic Pd-bound CO, as well as by the appearance of IR bands associated with CO2 adsorption as a function of annealing temperature. Samples containing oxidized Pd species (oxidized, annealed or reduced) always produced CO2 upon their exposure to CO, while CO2-related surface entities were observed on samples having only fully reduced (metallic) Pd. Acknowledgements: The catalyst preparation was supported by a Laboratory Directed Research and Development (LDRD) project. This work was supported by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).« less

Distributions of Beryllium 7 and Lead 210, and Soluble Aerosol-Associated Ionic Species Over the Western Pacific: PEM West B, February - March 1994

NASA Technical Reports Server (NTRS)

Dibb, J. E.; Talbot, R. W.; Lefer, B. L.; Scheuer, E.; Gregory, G. L.; Browell, E. V.; Bradshaw, J. D.; Sandholm, S. T.; Singh, H. B.

1997-01-01

Aerosol sampling for the determination of the concentrations of soluble ionic species and the natural radionuclides Be-7 and Pb-210 was conducted from the NASA DC-8 over the western Pacific as part of GTE/PEM-West B during February - March 1994. Concentrations of most soluble ionic species in the free troposphere were higher in samples collected on flights originating from Hong Kong and Japan than those collected further east over the open ocean. In both regions the measured concentrations were higher than those found during PEM-West A (fall 1991). Activities of Pb-210, a tracer of air masses influenced by sources on the Asian continent, showed the same patterns. These data indicate the effect of stronger continental outflow from Asia over the western Pacific during the spring compared to fall season. For readily scavenged aerosol-associated species and soluble acidic gases the strongest indications of Asian outflow were restricted to altitudes below 6 km. The distribution of the continental tracer Pb-210 was also compared to those of a large number of gas phase species measured on the DC-8. Relatively strong correlations were found with O3, and peroxyacetylnitrate (PAN), but only during the flights over the remote Pacific. During PEM-West A, similar correlations were seen, but they were stronger near Asia. We believe that correlations are a signature of continental air that has been processed by deep wet convection over land before being advected over the ocean. One flight over the Sea of Japan provided the opportunity to sample upper troposphere/lower stratosphere air in and around a tropopause fold. Concentrations of Be-7 reached 7 pCi/cu m STP, and peak O3, mixing ratios of 480 ppb were encountered at 10.7 km. The Be-7 data are used to estimate the fraction of stratospheric air mixed down into the troposphere by circulation in the fold.

Distributions of Beryllium 7 and Lead 210, and Soluble Aerosol-Associated Ionic Species Over the Western Pacific: PEM West B

NASA Technical Reports Server (NTRS)

Didd, J. E.; Talbot, R. W.; Lefer, B. L.; Scheuer, E.; Gregory, G. L.; Browell, E. V.; Sandholm, S. T.; Singh, H. B.

1997-01-01

Aerosol sampling for the determination of the concentrations of soluble ionic species and the natural radionuclides Be-7 and Pb-210 was conducted from the NASA DC-8 over the western Pacific as part of GTE/PEM-West B during February - March 1994. Concentrations of most soluble ionic species in the free troposphere were higher in samples collected on flights originating from Hong Kong and Japan than those collected further east over the open ocean. In both regions the measured concentrations were higher than those found during PEM-West A (fall 1991). Activities of Pb-210 tracer of air masses influenced by sources on the Asian continent, showed the same patterns. These data indicate the effect of stronger continental outflow from Asia over the western Pacific during the spring compared to fall season. For readily scavenged aerosol-associated species and soluble acidic gases the strongest indications of Asian outflow were restricted to altitudes below 6 km. The distribution of the continental tracer Pb-210 was also compared to those of a large number of gas phase species measured on the DC-8. Relatively strong correlations were found with O3 and peroxyacetylnitrate (PAN), but only during the flights over the remote Pacific. During PEM-West A, similar correlations were seen, but they were stronger near Asia. We believe that these correlations are a signature of continental air that has been processed by deep wet convection over land before being advected over the ocean. One flight over the Sea of Japan provided the opportunity to sample upper troposphere/lower stratosphere air in and around a tropopause fold. Concentrations of Be-7 reached 7 pCi/cu m STP, and peak O3, mixing ratios of 480 ppb were encountered at 10.7 km. The Be-7 data are used to estimate the fraction of stratospheric air mixed down into the troposphere by circulation in the fold.

Research on the properties and interactions of simple atomic and ionic systems

NASA Technical Reports Server (NTRS)

Novick, R.

1972-01-01

Simple ionic systems were studied, such as metastable autoionizing states of the negative He ion, two-photon decay spectrum of metastable He ion, optical excitation with low energy ions, and lifetime measurements of singly ionized Li and metastable He ion. Simple atomic systems were also investigated. Metastable autoionizing atomic energy levels in alkali elements were included, along with lifetime measurements of Cr-53, group 2A isotopes, and alkali metal atoms using level crossing and optical double resonance spectroscopy.

Multifunctional Poro-Vascular Composites for UAV Performance Enhancement

DTIC Science & Technology

2012-07-31

structural “skin” materials with surface pores and internal vascular channels filled with an ionic- liquid whose height and shape at the pore exits is...2 V t e e q q          Intrinsic contact angle (zero voltage) Applied potential Interfacial tension (IFT) of ionic liquid Lippmann...Characterization flat plates  single (capillary) pore  PV pore arrays FTA 1000 Drop-Shape Characterization • Microscope lens : 0.5 to 12x magnification • Side

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

2017-09-11

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Effects of electrostatic interactions on ligand dissociation kinetics

NASA Astrophysics Data System (ADS)

Erbaş, Aykut; de la Cruz, Monica Olvera; Marko, John F.

2018-02-01

We study unbinding of multivalent cationic ligands from oppositely charged polymeric binding sites sparsely grafted on a flat neutral substrate. Our molecular dynamics simulations are suggested by single-molecule studies of protein-DNA interactions. We consider univalent salt concentrations spanning roughly a 1000-fold range, together with various concentrations of excess ligands in solution. To reveal the ionic effects on unbinding kinetics of spontaneous and facilitated dissociation mechanisms, we treat electrostatic interactions both at a Debye-Hückel (DH) (or implicit ions, i.e., use of an electrostatic potential with a prescribed decay length) level and by the more precise approach of considering all ionic species explicitly in the simulations. We find that the DH approach systematically overestimates unbinding rates, relative to the calculations where all ion pairs are present explicitly in solution, although many aspects of the two types of calculation are qualitatively similar. For facilitated dissociation (FD) (acceleration of unbinding by free ligands in solution) explicit-ion simulations lead to unbinding at lower free-ligand concentrations. Our simulations predict a variety of FD regimes as a function of free-ligand and ion concentrations; a particularly interesting regime is at intermediate concentrations of ligands where nonelectrostatic binding strength controls FD. We conclude that explicit-ion electrostatic modeling is an essential component to quantitatively tackle problems in molecular ligand dissociation, including nucleic-acid-binding proteins.

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Molten Bis(trifluoromethylsulfonyl)amide Salts: Effects of Cation Species.

PubMed

Kakinuma, Shohei; Shirota, Hideaki

2018-05-25

In this study, we have investigated the effects of cation structures on the temperature dependence of the intermolecular vibrational dynamics of ionic liquids using femtosecond Raman-induced Kerr effect spectroscopy. The ionic liquids used in this study are bis(trifluoromethylsulfonyl)amide [NTf 2 ] - salts of the cations 1-butyl-3-methylimidazolium [C 4 MIm] + , 1-butyl-1-methylpyrrolidinium [Pyrr 14 ] + , 1-butylpyridinium [C 4 Py] + , butyldiethylmethylammonium [N 1224 ] + , triethyloctylammonium [N 2228 ] + , and triethyloctylphosphonium [P 2228 ] + . All of the ionic liquids show temperature-dependent low-frequency spectra. A difference in the temperature dependence between the spectra of the aromatic and nonaromatic cation based ionic liquids is especially significant. In the case of the aromatic cation based ionic liquids [C 4 MIm][NTf 2 ] and [C 4 Py][NTf 2 ], the spectral intensities in the low-frequency region below ca. 50 cm -1 increase and the high-frequency components at ca. 80 cm -1 shift to lower frequencies with rising temperature. In contrast, the ionic liquids based on nonaromatic cations only exhibit an increase in the low-frequency region below ca. 50 cm -1 with increasing temperature, while the high-frequency region of the spectra above ca. 50 cm -1 shows little change with variation of the temperature. These results suggest that the presence or absence of aromatic rings is the main factor in determining the temperature-dependent spectral features, particularly in the high-frequency region. We also found that the alkyl chain length and central atoms of the nonaromatic quaternary cations do not have much influence on the temperature-dependent spectral features. The first moments of the aromatic cation based ionic liquids are a little more sensitive to temperature than those of the nonaromatic cation based ionic liquids. The temperature-dependent viscosities and fragilities of the ionic liquids have also been examined.

The Influence of the Interlayer Distance on the Performance of Thermally Reduced Graphene Oxide Supercapacitors.

PubMed

Lin, Jun-Hong

2018-02-08

In this paper, cationic surfactant cetyltrimethylammonium bromide (CTAB) was employed to prevent the restack of the thermally reduce graphene oxide (TRG) sheets. A facile approach was demonstrated to effectively enlarge the interlayer distance of the TRG sheets through the ionic interaction between the intercalated CTAB and ionic liquids (ILs). The morphology of the composites and the interaction between the intercalated ionic species were systematically characterized by SEM, SAXS, XRD, TGA, and FTIR. In addition, the performance of the EDLC cells based on these TRG composites was evaluated. It was found that due to the increased interlayer distance (0.41 nm to 2.51 nm) that enlarges the accessible surface area for the IL electrolyte, the energy density of the cell can be significantly improved (23.1 Wh/kg to 62.5 Wh/kg).

The lanthanum gallate-based mixed conducting perovskite ceramics

NASA Astrophysics Data System (ADS)

Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

2005-01-01

The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

The Influence of the Interlayer Distance on the Performance of Thermally Reduced Graphene Oxide Supercapacitors

PubMed Central

Lin, Jun-Hong

2018-01-01

In this paper, cationic surfactant cetyltrimethylammonium bromide (CTAB) was employed to prevent the restack of the thermally reduce graphene oxide (TRG) sheets. A facile approach was demonstrated to effectively enlarge the interlayer distance of the TRG sheets through the ionic interaction between the intercalated CTAB and ionic liquids (ILs). The morphology of the composites and the interaction between the intercalated ionic species were systematically characterized by SEM, SAXS, XRD, TGA, and FTIR. In addition, the performance of the EDLC cells based on these TRG composites was evaluated. It was found that due to the increased interlayer distance (0.41 nm to 2.51 nm) that enlarges the accessible surface area for the IL electrolyte, the energy density of the cell can be significantly improved (23.1 Wh/kg to 62.5 Wh/kg). PMID:29419773

Phytoremediation of Ionic and Methyl Mercury Pollution

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

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant.« less

The interaction of an ionizing ligand with enzymes having a single ionizing group. Implications for the reaction of folate analogues with dihydrofolate reductase.

PubMed

Stone, S R; Morrison, J F

1983-06-29

Binding theory has been developed for the reaction of an ionizing enzyme with an ionizing ligand. Consideration has been given to the most general scheme in which all possible reactions and interconversions occur as well as to schemes in which certain interactions do not take place. Equations have been derived in terms of the variation of the apparent dissociation constant (Kiapp) as a function of pH. These equations indicate that plots of pKiapp against pH can be wave-, half-bell- or bell-shaped according to the reactions involved. A wave is obtained whenever there is formation of the enzyme-ligand complexes, ionized enzyme . ionized ligand and protonated enzyme . protonated ligand. The additional formation of singly protonated enzyme-ligand complexes does not affect the wave form of the plot, but can influence the shape of the overall curve. The formation of either ionized enzyme . ionized ligand or protonated enzyme . protonated ligand, with or without singly protonated enzyme-ligand species, gives rise to a half-bell-shaped plot. If only singly protonated enzyme-ligand complexes are formed the plots are bell-shaped, but it is not possible to deduce the ionic forms of the reactants that participate in complex formation. Depending on the reaction pathways, true values for the ionization and dissociation constants may or may not be determined.

On the importance of simultaneous infrared/fiber-optic temperature monitoring in the microwave-assisted synthesis of ionic liquids.

PubMed

Obermayer, David; Kappe, C Oliver

2010-01-07

The temperature profiles obtained from both an external infrared and internal fiber-optic sensor were compared for heating and synthesizing the ionic liquid 1-butyl-3-methylimidazolium bromide (bmimBr) under microwave conditions. Utilizing a single-mode microwave reactor that allows simultaneous infrared/fiber-optic temperature measurements, significant differences between the two methods of temperature monitoring were revealed. Due to the strong microwave absorptivity of ionic liquids and the delay experienced in monitoring temperature on the outer surface of a heavy-walled glass vial, external infrared temperature sensors can not be used to accurately control the temperature in the heating of ionic liquids under microwave conditions. The use of internal fiber-optic probes allows the monitoring and control of the heating behavior in a much better way. In order to prevent the strong exotherm in the synthesis of bmimBr under microwave conditions the use of a reaction vessel made out of silicon carbide is the method of choice. Because of the high thermal conductivity and effusivity of silicon carbide, the heat generated during the ionic liquid formation is efficiently exchanged with the comparatively cool air in the microwave cavity via the silicon carbide ceramic.

Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

PubMed Central

Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

2016-01-01

We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

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.

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

Recent experimental studies measured the ionic conductivities of a series of poly(glycidyl ether)s with varying neat dielectric constants (ɛ), viscosities (η), and glass transition temperatures (Tg), as hosts for lithium bistrifluoromethanesulfonimide (LiTFSI) salt. In such a context, it was demonstrated that the ionic conductivity of these polymer electrolytes was a function of ɛ rather than Tg or η, suggesting that there may exist regimes in which ionic conductivity is not limited by slow segmental dynamics but rather by low ionic dissociation. Motivated by such results, we used atomistic molecular dynamics to study the structure and transport characteristics of the same set of host polymers. We found that the coordination number of TFSI- about Li+ in the first solvation shell and the total fraction of free ions increased as a function of ɛ, implying the polymer hosts enhanced ion dissociation. In addition, we found that increasing the dielectric constant of the host polymer enhanced self-correlated ion transport, as evidenced by an increase in the diffusion coefficients of each ion species. Overall, we confirmed that limited ion dissociation in low- ɛ polymer electrolyte hosts hampers ionic conductivity. We would like to thank the National Science Foundation Graduate Research Fellowship Program for funding this research endeavor.

A novel hydroxyapatite film coated with ionic silver via inositol hexaphosphate chelation prevents implant-associated infection

NASA Astrophysics Data System (ADS)

Funao, Haruki; Nagai, Shigenori; Sasaki, Aya; Hoshikawa, Tomoyuki; Tsuji, Takashi; Okada, Yasunori; Koyasu, Shigeo; Toyama, Yoshiaki; Nakamura, Masaya; Aizawa, Mamoru; Matsumoto, Morio; Ishii, Ken

2016-03-01

Various silver-coated implants have been developed to prevent implant-associated infections, and have shown dramatic effects in vitro. However, the in vivo results have been inconsistent. Recent in vitro studies showed that silver exerts antibacterial activity by mediating the generation of reactive oxygen species in the presence of oxygen. To maintain its antibacterial activity in vivo, the silver should remain in an ionic state and be stably bound to the implant surface. Here, we developed a novel bacteria-resistant hydroxyapatite film in which ionic silver is immobilized via inositol hexaphosphate chelation using a low-heat immersion process. This bacteria-resistant coating demonstrated significant antibacterial activity both in vitro and in vivo. In a murine bioluminescent osteomyelitis model, no bacteria were detectable 21 days after inoculation with S. aureus and placement of this implant. Serum interleukin-6 was elevated in the acute phase in this model, but it was significantly lower in the ionic-silver group than the control group on day 2. Serum C-reactive protein remained significantly higher in the control group than the ionic-silver group on day 14. Because this coating is produced by a low-heat immersion process, it can be applied to complex structures of various materials, to provide significant protection against implant-associated infections.

Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko

2000-08-01

The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.

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.

Effect of Multivalent Ions on Electroosmotic Flow in Micro- and Nano-channels

NASA Astrophysics Data System (ADS)

Zheng, Zhi; Conlisk, A. Terrence

2002-11-01

In this work, the effect of multivalent ions on electroosmotic flow is investigated. Applications in biomedical engineering are numerous, including design of drug delivery systems, rapid molecular analysis and lab-on-a-chip. We specifically consider incorporating Ca^2+ and HPO4^2- and other monovalent ions, such as K^+ and H2PO4^-, into an aqueous NaCl solution. All previous work has been for the case where the mixture contains a pair of ionic species of equal valence. Electrochemical equilibrium considerations are used in determining the boundary conditions. The results can be applied to rectangular channels for which the height is on the nanometer scale up to the micrometer scale. The classical electroosmotic velocity profile is obtained at larger channel heights for fixed electrolyte concentration where an analytic solution for the velocity, potential and mole fractions may be obtained. The theory is valid for an arbitrary number of ionic species.

Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis.

PubMed

Fukai, Nao; Kitagawa, Shinya; Ohtani, Hajime

2017-07-01

We have recently demonstrated the separation of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis (NACZE) using a cationic surfactant of cetyltrimethylammonium chloride (CTAC). In this study, eight ionic surfactants were investigated for the separation of four synthetic polymers (polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate); only three surfactants (CTAC, dimethyldioctadecylammonium bromide, and sodium dodecylsulfate) caused their separation. The order of the interaction between the polymers and the surfactants depended on both the surfactant species and the composition of the electrophoretic medium. Their investigation revealed that the separation is majorly affected by the hydrophobic interactions between the polymers and the ionic surfactants. In addition, the electrophoretic behavior of polycarbonate suggested that electrostatic interaction also affects the selectivity of the polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive

PubMed Central

Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing

2016-01-01

Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene–conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions. PMID:27386541

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.

Amino acid anions in organic ionic compounds. An ab initio study of selected ion pairs.

PubMed

Benedetto, A; Bodo, E; Gontrani, L; Ballone, P; Caminiti, R

2014-03-06

The combination of amino acids in their deprotonated and thus anionic form with a choline cation gives origin to a new and potentially important class of organic ionic compounds. A series of such neutral ion pairs has been investigated by first principle methods. The results reveal intriguing structural motives as well as regular patterns in the charge distribution and predict a number of vibrational and optical properties that could guide the experimental investigation of these compounds. The replacement of choline with its phosphocholine analogue causes the spontaneous reciprocal neutralization of cations and anions, taking place through the transfer of a proton between the two ions. Systems of this kind, therefore, provide a wide and easily accessible playground to probe the ionic/polar transition in organic systems, while the easy transfer of H(+) among neutral and ionic species points to their potential application as proton conductors. The analysis of the ab initio data highlights similarities as well as discrepancies from the rigid-ions force-field picture and suggests directions for the improvement of empirical models.

The active modulation of drug release by an ionic field effect transistor for an ultra-low power implantable nanofluidic system.

PubMed

Bruno, Giacomo; Canavese, Giancarlo; Liu, Xuewu; Filgueira, Carly S; Sacco, Adriano; Demarchi, Danilo; Ferrari, Mauro; Grattoni, Alessandro

2016-11-10

We report an electro-nanofluidic membrane for tunable, ultra-low power drug delivery employing an ionic field effect transistor. Therapeutic release from a drug reservoir was successfully modulated, with high energy efficiency, by actively adjusting the surface charge of slit-nanochannels 50, 110, and 160 nm in size, by the polarization of a buried gate electrode and the consequent variation of the electrical double layer in the nanochannel. We demonstrated control over the transport of ionic species, including two relevant hypertension drugs, atenolol and perindopril, that could benefit from such modulation. By leveraging concentration-driven diffusion, we achieve a 2 to 3 order of magnitude reduction in power consumption as compared to other electrokinetic phenomena. The application of a small gate potential (±5 V) in close proximity (150 nm) of 50 nm nanochannels generated a sufficiently strong electric field, which doubled or blocked the ionic flux depending on the polarity of the voltage applied. These compelling findings can lead to next generation, more reliable, smaller, and longer lasting drug delivery implants with ultra-low power consumption.

Ion Dynamics in a Mixed-Cation Alkoxy-Ammonium Ionic Liquid Electrolyte for Sodium Device Applications.

PubMed

Pope, Cameron R; Kar, Mega; MacFarlane, Douglas R; Armand, Michel; Forsyth, Maria; O'Dell, Luke A

2016-10-18

The ion dynamics in a novel sodium-containing room-temperature ionic liquid (IL) consisting of an ether-functionalised quaternary ammonium cation and bis(trifluoromethylsulfonyl)amide [NTf 2 ] anion with various concentrations of Na[NTf 2 ] have been characterised using differential scanning calorimetry, impedance spectroscopy, diffusometry and NMR relaxation measurements. The IL studied has been specifically designed to dissolve a relatively large concentration of Na[NTf 2 ] salt (over 2 mol kg -1 ) as this has been shown to improve ion transport and conductivity. Consistent with other studies, the measured ionic conductivity and diffusion coefficients show that the overall ionic mobility decreases with decreasing temperature and increasing salt content. NMR relaxation measurements provide evidence for correlated dynamics between the ether-functionalised ammonium and Na cations, possibly with the latter species acting as cross-links between multiple ammonium cations. Finally, preliminary cyclic voltammetry experiments show that this IL can undergo stable electrochemical cycling and could therefore be potentially useful as an electrolyte in a Na-based device. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for forming cooperative binary ionic solids

DOEpatents

Shelnutt, John A.; Martin, Kathleen E.; Wang, Zhongchun; Medforth, Craig J.

2013-03-05

A nanostructured molecular unit and method for forming is described where a cationic porphyrin having an ethanolic substituent species and a metal in the porphyrin cavity is combined with an anionic porphyrin having a sulfonate substituent species and a metal in the porphyrin cavity to form by self-assembly a nanostructured molecular unit with a morphology comprising four dendritic elements connected at a central node.

Method for forming cooperative binary ionic solids

DOEpatents

Shelnutt, John A.; Martin, Kathleen E.; Wang, Zhongchun; Medforth, Craig J.

2014-09-09

A nanostructured molecular unit and method for forming is described where a cationic porphyrin having an ethanolic substituent species and a metal in the porphyrin cavity is combined with an anionic porphyrin having a sulfonate substituent species and a metal in the porphyrin cavity to form by self-assembly a nanostructured molecular unit with a morphology comprising four dendritic elements connected at a central node.

Ultrafast fluorescence upconversion technique and its applications to proteins.

PubMed

Chosrowjan, Haik; Taniguchi, Seiji; Tanaka, Fumio

2015-08-01

The basic principles and main characteristics of the ultrafast time-resolved fluorescence upconversion technique (conventional and space-resolved), including requirements for nonlinear crystals, mixing spectral bandwidth, acceptance angle, etc., are presented. Applications to flavoproteins [wild-type (WT) FMN-binding protein and its W32Y, W32A, E13R, E13K, E13Q and E13T mutants] and photoresponsive proteins [WT photoactive yellow protein and its R52Q mutant in solution and as single crystals] are demonstrated. For flavoproteins, investigations elucidating the effects of ionic charges on ultrafast electron transfer (ET) dynamics are summarized. It is shown that replacement of the ionic amino acid Glu13 and the resulting modification of the electrostatic charge distribution in the protein chromphore-binding pocket substantially alters the ultrafast fluorescence quenching dynamics and ET rate in FMN-binding protein. It is concluded that, together with donor-acceptor distances, electrostatic interactions between ionic photoproducts and other ionic groups in the proteins are important factors influencing the ET rates. In WT photoactive yellow protein and the R52Q mutant, ultrafast photoisomerization dynamics of the chromophore (deprotonated trans-p-coumaric acid) in liquid and crystal phases are investigated. It is shown that the primary dynamics in solution and single-crystal phases are quite similar; hence, the photocycle dynamics and structural differences observed at longer time scales arise mostly from the structural restraints imposed by the crystal lattice rigidity versus the flexibility in solution. © 2014 FEBS.

Does titanium in ionic form display a tissue-specific distribution?

PubMed

Golasik, Magdalena; Wrobel, Pawel; Olbert, Magdalena; Nowak, Barbara; Czyzycki, Mateusz; Librowski, Tadeusz; Lankosz, Marek; Piekoszewski, Wojciech

2016-06-01

Most studies have focused on the biodistribution of titanium(IV) oxide as nanoparticles or crystals in organism. But several reports suggested that titanium is released from implant in ionic form. Therefore, gaining insight into toxicokinetics of Ti ions will give valuable information, which may be useful when assessing the health risks of long-term exposure to titanium alloy implants in patients. A micro synchrotron radiation-induced X-ray fluorescence (µ-SRXRF) was utilized to investigate the titanium distribution in the liver, spleen and kidneys of rats following single intravenous or 30-days oral administration of metal (6 mg Ti/b.w.) in ionic form. Titanium was mainly retained in kidneys after both intravenous and oral dosing, and also its compartmentalization in this organ was observed. Titanium in the liver was non-uniformly distributed-metal accumulated in single aggregates, and some of them were also enriched in calcium. Correlation analysis showed that metal did not displace essential elements, and in liver titanium strongly correlated with calcium. Two-dimensional maps of Ti distribution show that the location of the element is characteristic for the route of administration and time of exposure. We demonstrated that µ-SRXRF can provide information on the distribution of titanium in internal structures of whole organs, which helps in enhancing our understanding of the mechanism of ionic titanium accumulation in the body. This is significant due to the popularity of titanium implants and the potential release of metal ions from them to the organism.

Effect of dipolar moments in domain sizes of lipid bilayers and monolayers

NASA Astrophysics Data System (ADS)

Travesset, A.

2006-08-01

Lipid domains are found in systems such as multicomponent bilayer membranes and single component monolayers at the air-water interface. It was shown by Keller et al. [J. Phys. Chem. 91, 6417 (1987)] that in monolayers, the size of the domains results from balancing the line tension, which favors the formation of a large single circular domain, against the electrostatic cost of assembling the dipolar moments of the lipids. In this paper, we present an exact analytical expression for the electric potential, ion distribution, and electrostatic free energy for different problems consisting of three different slabs with different dielectric constants and Debye lengths, with a circular homogeneous dipolar density in the middle slab. From these solutions, we extend the calculation of domain sizes for monolayers to include the effects of finite ionic strength, dielectric discontinuities (or image charges), and the polarizability of the dipoles and further generalize the calculations to account for domains in lipid bilayers. In monolayers, the size of the domains is dependent on the different dielectric constants but independent of ionic strength. In asymmetric bilayers, where the inner and outer leaflets have different dipolar densities, domains show a strong size dependence with ionic strength, with molecular-sized domains that grow to macroscopic phase separation with increasing ionic strength. We discuss the implications of the results for experiments and briefly consider their relation to other two dimensional systems such as Wigner crystals or heteroepitaxial growth.

Effects of Ionic Dependence of DNA Persistence Length on the DNA Condensation at Room Temperature

NASA Astrophysics Data System (ADS)

Mao, Wei; Liu, Yan-Hui; Hu, Lin; Xu, Hou-Qiang

2016-05-01

DNA persistence length is a key parameter for quantitative interpretation of the conformational properties of DNA and related to the bending rigidity of DNA. A series of experiments pointed out that, in the DNA condensation process by multivalent cations, the condensed DNA takes elongated coil or compact globule states and the population of the compact globule states increases with an increase in ionic concentration. At the same time, single molecule experiments carried out in solution with multivalent cations (such as spermidine, spermine) indicated that DNA persistence length strongly depends on the ionic concentration. In order to revolve the effects of ionic concentration dependence of persistence length on DNA condensation, a model including the ionic concentration dependence of persistence length and strong correlation of multivalent cation on DNA is provided. The autocorrelation function of the tangent vectors is found as an effective way to detect the ionic concentration dependence of toroidal conformations. With an increase in ion concentration, the first periodic oscillation contained in the autocorrelation function shifts, the number of segment contained in the first periodic oscillation decreases gradually. According to the experiments, the average long-axis length is defined to estimate the ionic concentration dependence of condensation process further. The relation between long-axis length and ionic concentration matches the experimental results qualitatively. Supported by National Natural Science Foundation of China under Grant Nos. 11047022, 11204045, 11464004 and 31360215; The Research Foundation from Ministry of Education of China (212152), Guizhou Provincial Tracking Key Program of Social Development (SY20123089, SZ20113069); The General Financial Grant from the China Postdoctoral Science Foundation (2014M562341); The Research Foundation for Young University Teachers from Guizhou University (201311); The West Light Foundation (2015) and College Innovation Talent Team of Guizhou Province, (2014) 32

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study.

PubMed

Patel, Salin Gupta; Bummer, Paul M

2017-01-10

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K-100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (C sat ) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔH agg ° , ΔG agg ° , H agg ° , ΔS agg ° , and ΔC p were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis.

PubMed

Ruiz, Elia; Ferro, Victor R; Palomar, Jose; Ortega, Juan; Rodriguez, Juan Jose

2013-06-20

The interactions between ionic liquids (ILs) and acetone have been studied to obtain a further understanding of the behavior of their mixtures, which generally give place to an exothermic process, mutual miscibility, and negative deviation of Raoult's law. COSMO-RS was used as a suitable computational method to systematically analyze the excess enthalpy of IL-acetone systems (>300), in terms of the intermolecular interactions contributing to the mixture behavior. Spectroscopic and COSMO-RS results indicated that acetone, as a polar compound with strong hydrogen bond acceptor character, in most cases, establishes favorable hydrogen bonding with ILs. This interaction is strengthened by the presence of an acidic cation and an anion with dispersed charge and non-HB acceptor character in the IL. COSMO-RS predictions indicated that gas-liquid and vapor-liquid equilibrium data for IL-acetone systems can be finely tuned by the IL selection, that is, acting on the intermolecular interactions between the molecular and ionic species in the liquid phase. NMR measurements for IL-acetone mixtures at different concentrations were also carried out. Quantum-chemical calculations by using molecular clusters of acetone and IL species were finally performed. These results provided additional evidence of the main role played by hydrogen bonding in the behavior of systems containing ILs and HB acceptor compounds, such as acetone.

[CuCl(n)](2-n) ion-pair species in 1-ethyl-3-methylimidazolium chloride ionic liquid-water mixtures: ultraviolet-visible, X-ray absorption fine structure, and density functional theory characterization.

PubMed

Li, Guosheng; Camaioni, Donald M; Amonette, James E; Zhang, Z Conrad; Johnson, Timothy J; Fulton, John L

2010-10-07

We studied the coordination environment about Cu(II) in a pure ionic liquid, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), and in binary mixtures of this compound with water across the entire range of compositions, using a combination of X-ray absorption fine structure (XAFS), ultraviolet-visible (UV-vis) spectroscopy, and electronic structure calculations. Our results show a series of stages in the ion pairing of the divalent cation, Cu(II), including the contact ion pairing of Cu(2+) with multiple Cl(-) ligands to form various CuCl(n)((2-n)) polyanions, as well as the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM(+) cation. Ion-pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen-bond network in [EMIM]Cl-water mixtures. The CuCl(4)(2-) species dominates in the [EMIM]Cl solvent, and calculations along with spectroscopy show that its geometry distorts to C(2) symmetry compared to D(2d) in the gas phase. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.

Ab initio study of the structural properties of ascorbic acid (vitamin C)

NASA Astrophysics Data System (ADS)

Allen, Reeshemah N.; Shukla, M. K.; Reed, Demarcio; Leszczynski, Jerzy

Geometries of the neutral and ionic tautomeric species of ascorbic acid were optimized at the density functional theory (DFT) level using the B3LYP functional. The radical species were evaluated using the unrestricted B3LYP method. Single-point energy calculations were also performed using the Møller-Plesset (MP2) and unrestricted MP2 (UMP2) methods for the closed-shell and open-shell systems, respectively. The effects of aqueous solution were evaluated using the conducting polarized continuum model (CPCM) and polarized continuum model (PCM). The geometries of most stable radicals in the respective groups were also optimized in the water solution using the CPCM model at the UB3LYP level. All calculation were performed using the 6-311++G(d,p) basis set. The nature of stationary points on the gas phase potential energy surfaces (PESs) was evaluated using vibrational frequency calculations; all geometries characterize local minima. The species obtained by the deprotonation of the O3 site is the most stable monoanion of ascorbic acid. For the radical species, the structure obtained by the dehydrogenation of the O3 site is the most stable monoradical. Among the radical anions, the species obtained by the deprotonation of the O3 site and subsequent dehydrogenation of the O2 site is the most stable in the gas phase and in an aqueous medium. The computed isotropic hyperfine coupling constants of this species were found to be in good agreement with the experimental data. Our investigation also supports the earlier findings that the oxidized species of ascorbic acid in water solution by the OH? radical is radical anion of the AAO?3O-2 form. The spin densities and molecular electrostatic potentials are also discussed.

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

PubMed

Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

2011-08-14

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

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.

An electrochemical rebalance cell for Redox systems

NASA Technical Reports Server (NTRS)

Acevedo, J. C.; Stalnaker, D. K.

1983-01-01

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Ion sensing method

DOEpatents

Smith, Richard Harding; Martin, Glenn Brian

2004-05-18

The present invention allows the determination of trace levels of ionic substances in a sample solution (ions, metal ions, and other electrically charged molecules) by coupling a separation method, such as liquid chromatography, with ion selective electrodes (ISE) prepared so as to allow detection at activities below 10.sup.-6 M. The separation method distributes constituent molecules into fractions due to unique chemical and physical properties, such as charge, hydrophobicity, specific binding interactions, or movement in an electrical field. The separated fractions are detected by means of the ISE(s). These ISEs can be used singly or in an array. Accordingly, modifications in the ISEs are used to permit detection of low activities, specifically, below 10.sup.-6 M, by using low activities of the primary analyte (the molecular species which is specifically detected) in the inner filling solution of the ISE. Arrays constructed in various ways allow flow-through sensing for multiple ions.

First measurements of the temporal evolution of the plasma density in HiPIMS discharges using THz time domain spectroscopy

NASA Astrophysics Data System (ADS)

Meier, Steffen M.; Hecimovic, Ante; Tsankov, Tsanko V.; Luggenhölscher, Dirk; Czarnetzki, Uwe

2018-03-01

In this paper, the novel technique of THz time domain spectroscopy has been applied to obtain time-resolved measurements of the plasma density in the active zone of a HiPIMS discharge with a titanium target. The obtained peak values are in the range of 1012-1013 cm-3 for discharge current densities of 1-4 A cm-2 at 0.5 and 2 Pa argon pressure. The measured densities show good correlation with the discharge current and voltage and the intensity of various atomic and ionic lines. The well known phases of the discharge have been identified and related to the variation of the electron density. The measurement results show that the plasma density remains nearly constant during the runaway/self-sputtering phase. Based on that, it is conjectured that singly charged titanium ions are the dominant ion species during this phase.

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.

Enantioselective Organocatalytic Aminomethylation of Aldehydes: A Role for Ionic Interactions and Efficient Access to β2-Amino Acids

PubMed Central

Chi, Yonggui; Gellman, Samuel H.

2009-01-01

Organocatalytic Mannich addition of aldehydes to a formaldehyde-derived iminium species catalyzed by proline-derived chiral pyrrolidines provides β-amino aldehydes with ≥ 90% ee. Mechanistic analysis of the proline-catalyzed reactions suggests that non-hydrogen-bonded ionic interactions at the Mannich reaction transition state can influence stereochemical outcome. The β-amino aldehydes from our process bear a substituent adjacent to the carbonyl and can be efficiently converted to protected β2-amino acids, which are important building blocks for β-peptide foldamers that display useful biological activities. PMID:16719457

Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

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

Dittrich, Timothy M.; Richmann, Michael K.; Reed, Donald T.

2015-10-30

The degree of conservatism in the estimated sorption partition coefficients (K ds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

[Application of simultaneous determination of inorganic ionic species by advanced ion chromatography for water quality monitoring of river water and wastewater].

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

2012-04-01

In this study, our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions (SO4(2-), Cl(-) and NO3(-)) and cations (Na+, NH4+, K+, Mg2+, and Ca2+), nutrients (phosphate and silicate) and hydrogen ion/alkalinity are summarized first. Then, the applications using these methods for monitoring environmental water quality are also presented. For the determination of common anions and cations with nutrients, the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C (Tosoh, 150 mm x 6.0 mm i. d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry. For the determination of hydrogen ion/alkalinity, the separation was conducted by TSKgel ODS-100Z column (Tosoh, 150 mm x 4.5 mm i. d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector. The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant. Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed. From these results, our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.

The performance of fast-moving low-voltage electromechanical actuators based on single-walled carbon nanotubes and ionic liquids

NASA Astrophysics Data System (ADS)

Mukai, Ken; Asaka, Kinji; Hata, Kenji; Oike, Hideaki

2011-12-01

In this paper, we study the details of the mechanical and electrical properties of polymer-free single-walled carbon nanotube (SWNT) sheets containing different contents of ionic liquids (ILs). The polymer-free SWNT sheets were prepared by a previously reported finding that millimeter-long 'super-growth' carbon nanotubes (SG-SWNTs), produced by a water-assisted modified chemical vapor deposition (CVD) method, associate together tightly with ILs, affording a free-standing sheet with a superb conductivity. The Young's modulus, breaking strength and the electrical conductivity of the SG-SWNT sheet with 67 wt% 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) showed large values, 0.63 GPa, 20 MPa, and 147 S cm-1, respectively, although it has large amounts of ILs. We also measure the frequency dependence of the displacement of the actuator composed of SG-SWNT sheets sandwiching an ionic-gel electrolyte layer (SG-SWNT actuator). At more than 50 wt% of EMITFSI content, the frequency response of the actuation of the SG-SWNT actuator is flat up to around 100 Hz. The results of the displacement measurements are discussed in relation to the mechanical and electrical properties of the SG-SWNT actuators.

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.

An equivalent dipole analysis of PZT ceramics and lead-free piezoelectric single crystals

NASA Astrophysics Data System (ADS)

Bell, Andrew J.

2016-04-01

The recently proposed Equivalent Dipole Model for describing the electromechanical properties of ionic solids in terms of 3 ions and 2 bonds has been applied to PZT ceramics and lead-free single crystal piezoelectric materials, providing analysis in terms of an effective ionic charge and the asymmetry of the interatomic force constants. For PZT it is shown that, as a function of composition across the morphotropic phase boundary, the dominant bond compliance peaks at 52% ZrO2. The stiffer of the two bonds shows little composition dependence with no anomaly at the phase boundary. The effective charge has a maximum value at 50% ZrO2, decreasing across the phase boundary region, but becoming constant in the rhombohedral phase. The single crystals confirm that both the asymmetry in the force constants and the magnitude of effective charge are equally important in determining the values of the piezoelectric charge coefficient and the electromechanical coupling coefficient. Both are apparently temperature dependent, increasing markedly on approaching the Curie temperature.

Peracetic acid-ionic liquid pretreatment to enhance enzymatic saccharification of lignocellulosic biomass.

PubMed

Uju; Abe, Kojiro; Uemura, Nobuyuki; Oshima, Toyoji; Goto, Masahiro; Kamiya, Noriho

2013-06-01

To enhance enzymatic saccharification of pine biomass, the pretreatment reagents peracetic acid (PAA) and ionic liquid (IL) were validated in single reagent pretreatments or combination pretreatments with different sequences. In a 1h saccharification, 5-25% cellulose conversion was obtained from the single pretreatment of PAA or IL. In contrast, a marked enhancement in conversion rates was achieved by PAA-IL combination pretreatments (45-70%). The PAA followed by IL (PAA+IL) pretreatment sequence was the most effective for preparing an enzymatic digestible regenerated biomass with 250-fold higher glucose formation rates than untreated biomass and 2- to 12-fold higher than single pretreatments with PAA or IL alone. Structural analysis confirmed that this pretreatment resulted in biomass with highly porous structural fibers associated with the reduction of lignin content and acetyl groups. Using the PAA+IL sequence, biomass loading in the pretreatment step can be increased from 5% to 15% without significant decrease in cellulose conversion. Copyright © 2013 Elsevier Ltd. All rights reserved.

A classical density functional theory for the asymmetric restricted primitive model of ionic liquids

NASA Astrophysics Data System (ADS)

Lu, Hongduo; Nordholm, Sture; Woodward, Clifford E.; Forsman, Jan

2018-05-01

A new three-parameter (valency, ion size, and charge asymmetry) model, the asymmetric restricted primitive model (ARPM) of ionic liquids, has recently been proposed. Given that ionic liquids generally are composed of monovalent species, the ARPM effectively reduces to a two-parameter model. Monte Carlo (MC) simulations have demonstrated that the ARPM is able to reproduce key properties of room temperature ionic liquids (RTILs) in bulk and at charged surfaces. The relatively modest complexity of the model raises the possibility, which is explored here, that a classical density functional theory (DFT) could resolve its properties. This is relevant because it might generate great improvements in terms of both numerical efficiency and understanding in the continued research of RTILs and their applications. In this report, a DFT for rod-like molecules is proposed as an approximate theoretical tool for an ARPM fluid. Borrowing data on the ion pair fraction from a single bulk simulation, the ARPM is modelled as a mixture of dissociated ions and connected ion pairs. We have specifically studied an ARPM where the hard-sphere diameter is 5 Å, with the charge located 1 Å from the hard-sphere centre. We focus on fluid structure and electrochemical behaviour of this ARPM fluid, into which a model electrode is immersed. The latter is modelled as a perfect conductor, and surface polarization is handled by the method of image charges. Approximate methods, which were developed in an earlier study, to take image interactions into account, are also incorporated in the DFT. We make direct numerical comparisons between DFT predictions and corresponding simulation data. The DFT theory is implemented both in the normal mean field form with respect to the electrostatic interactions and in a correlated form based on hole formation by both steric repulsions and ion-ion Coulomb interactions. The results clearly show that ion-ion correlations play a very important role in the screening of the charged surfaces by our ARPM ionic liquid. We have studied electrostatic potentials and ion density profiles as well the differential capacitance. The mean-field DFT fails to reproduce these properties, but the inclusion of ion-ion correlation by a simple approximate treatment yields quite reasonable agreement with the corresponding simulation results. An interesting finding is that there appears to be a surface phase transition at relatively low surface charge which is readily explored by DFT, but seen also in the MC simulations at somewhat higher asymmetry.

AN EXACT METHOD FOR RELATING ZWITTERIONIC MICROSCOPIC TO MACROSCOPIC ACIDITY CONSTANTS

EPA Science Inventory

Zwitterions are aqueous solvated molecules simultaneously possessing one negatively and one positively charged site. Although electroneutral, the environmental interaction of zwitterions with other ionic species is likely to differ significantly from the behavior of comparable e...

Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes.

PubMed

Wang, Yong-Lei; Golets, Mikhail; Li, Bin; Sarman, Sten; Laaksonen, Aatto

2017-02-08

Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P 6,6,6,14 ][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P 6,6,6,14 ] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P 6,6,6,14 ] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel-perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P 6,6,6,14 ][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P 6,6,6,14 ] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm 2 ), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P 6,6,6,14 ] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel-perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.

Time of flight emission spectroscopy of laser produced nickel plasma: Short-pulse and ultrafast excitations

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

Smijesh, N.; Chandrasekharan, K.; Joshi, Jagdish C.

2014-07-07

We report the experimental investigation and comparison of the temporal features of short-pulse (7 ns) and ultrafast (100 fs) laser produced plasmas generated from a solid nickel target, expanding into a nitrogen background. When the ambient pressure is varied in a large range of 10⁻⁶Torr to 10²Torr, the plume intensity is found to increase rapidly as the pressure crosses 1 Torr. Time of flight (TOF) spectroscopy of emission from neutral nickel (Ni I) at 361.9 nm (3d⁹(²D) 4p → 3d⁹(²D) 4s transition) reveals two peaks (fast and slow species) in short-pulse excitation and a single peak in ultrafast excitation. Themore » fast and slow peaks represent recombined neutrals and un-ionized neutrals, respectively. TOF emission from singly ionized nickel (Ni II) studied using the 428.5 nm (3p⁶3d⁸(³P) 4s→ 3p⁶3d⁹ 4s) transition shows only a single peak for either excitation. Velocities of the neutral and ionic species are determined from TOF measurements carried out at different positions (i.e., at distances of 2 mm and 4 mm, respectively, from the target surface) on the plume axis. Measured velocities indicate acceleration of neutrals and ions, which is caused by the Coulomb pull of the electrons enveloping the plume front in the case of ultrafast excitation. Both Coulomb pull and laser-plasma interaction contribute to the acceleration in the case of short-pulse excitation. These investigations provide new information on the pressure dependent temporal behavior of nickel plasmas produced by short-pulse and ultrafast laser pulses, which have potential uses in applications such as pulsed laser deposition and laser-induced nanoparticle generation.« less

Tension in Skinned Frog Muscle Fibers in Solutions of Varying Ionic Strength and Neutral Salt Composition

PubMed Central

Gordon, A. M.; Godt, R. E.; Donaldson, S. K. B.; Harris, C. E.

1973-01-01

The maximal calcium-activated isometric tension produced by a skinned frog single muscle fiber falls off as the ionic strength of the solution bathing this fiber is elevated declining to zero near 0.5 M as the ionic strength is varied using KCl. When other neutral salts are used, the tension always declines at high ionic strength, but there is some difference between the various neutral salts used. The anions and cations can be ordered in terms of their ability to inhibit the maximal calcium-activated tension. The order of increasing inhibition of tension (decreasing tension) at high ionic strength for anions is propionate- ≃ SO4 -- < Cl- < Br-. The order of increasing inhibition of calcium-activated tension for cations is K+ ≃ Na+ ≃ TMA+ < TEA+ < TPrA+ < TBuA+. The decline of maximal calcium-activated isometric tension with elevated salt concentration (ionic strength) can quantitatively explain the decline of isometric tetanic tension of a frog muscle fiber bathed in a hypertonic solution if one assumes that the internal ionic strength of a muscle fiber in normal Ringer's solution is 0.14–0.17 M. There is an increase in the base-line tension of a skinned muscle fiber bathed in a relaxing solution (no added calcium and 3 mM EGTA) of low ionic strength. This tension, which has no correlate in the intact fiber in hypotonic solutions, appears to be a noncalcium-activated tension and correlates more with a declining ionic strength than with small changes in [MgATP], [Mg], pH buffer, or [EGTA]. It is dependent upon the specific neutral salts used with cations being ordered in increasing inhibition of this noncalcium-activated tension (decreasing tension) as TPrA+ < TMA+ < K+ ≃ Na+. Measurements of potentials inside these skinned muscle fibers bathed in relaxing solutions produced occasional small positive values (<6 mV) which were not significantly different from zero. PMID:4543066

Determination of Inorganic Ion Profiles of Illicit Drugs by Capillary Electrophoresis.

PubMed

Evans, Elizabeth; Costrino, Carolina; do Lago, Claudimir L; Garcia, Carlos D; Roux, Claude; Blanes, Lucas

2016-11-01

A portable capillary electrophoresis instrument with dual capacitively coupled contactless conductivity detection (C 4 D) was used to determine the inorganic ionic profiles of three pharmaceutical samples and precursors of two illicit drugs (contemporary samples of methylone and para-methoxymethamphetamine). The LODs ranged from 0.10 μmol/L to 1.25 μmol/L for the 10 selected cations, and from 0.13 μmol/L to 1.03 μmol/L for the eight selected anions. All separations were performed in less than 6 min with migration times and peak area RSD values ranging from 2 to 7%. The results demonstrate the potential of the analysis of inorganic ionic species to aid in the identification and/or differentiation of unknown tablets, and real samples found in illicit drug manufacture scenarios. From the resulting ionic fingerprint, the unknown tablets and samples can be further classified. © 2016 American Academy of Forensic Sciences.

Peroxyoxalate chemiluminescence enhanced by oligophenylenevinylene fluorophores in the presence of various surfactants.

PubMed

Motoyoshiya, Jiro; Takigawa, Setsuko

2014-11-01

The effect of several surfactants on peroxyoxalate chemiluminescence (PO-CL) using oligophenylenevinylene fluorophores was investigated. Among several oligophenylenevinylenes consisting of stilbene units, linearly conjugated ones, such as distyrylbenzene and distyrylstilbene, effectively enhanced PO-CL efficiency. Various effects of anionic, cationic, amphoteric and non-ionic surfactants on the CL efficiency of PO-CL were determined using three oxalates and the distyrylbenzene fluorophore. Anionic and non-ionic surfactants effectively enhanced CL efficiency, in contrast to the negative effect of cationic and amphoteric surfactants. Non-ionic surfactants were also effective in CL reactions of oxalates bearing dodecyl ester groups by the hydrophobic interaction between their alkyl chains. Considering these results, the surfactants not only increase the concentrations of water-insoluble interacting species in the hydrophobic micelle cores, but also control rapid degradation of the oxalates by alkaline hydrolysis. Copyright © 2014 John Wiley & Sons, Ltd.

Structure and diffusion of furans and other cellulose-derived compounds in solvents via MD simulation

NASA Astrophysics Data System (ADS)

Rabideau, Brooks; Ismail, Ahmed

2011-03-01

There is now a large push towards the development of energy sources that are both environmentally friendly and sustainable; with the conversion of cellulose derived from biomass into biofuels being one promising route. In this conversion, a variety of intermediary compounds have been identified, which appear critical to successful expansion of the process to an industrial scale. Here we examine the structure and diffusion of these furans and acids derived from cellulose within ionic liquids via molecular dynamic simulation. Ionic liquids have shown the ability to dissolve cellulose with certain `green' benefits over existing, conventional solvents. Specifically, we study the solvation properties of these chemicals by examining the pair correlation functions of solute with solvent, and by exploring the agglomeration and separation of these chemicals from the solvent as well as the hydrogen bonding between species. Additionally, we determine the diffusion constant of these compounds in ionic liquid and aqueous solvents.

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.

A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

PubMed

Castro Grijalba, Alexander; Fiorentini, Emiliano F; Martinez, Luis D; Wuilloud, Rodolfo G

2016-09-02

The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00μg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties. Copyright © 2016 Elsevier B.V. All rights reserved.

Polar-interferometry: what can be learnt from the IOTA/IONIC experiment

NASA Astrophysics Data System (ADS)

Le Bouquin, Jean-Baptiste; Rousselet-Perraut, Karine; Berger, Jean-Philippe; Herwats, Emilie; Benisty, Myriam; Absil, Olivier; Defrere, Denis; Monnier, John; Traub, Wesley

2008-07-01

We report the first near-IR polar-interferometric observations, performed at the IOTA array using its integrated optics combiner IONIC. Fringes have been obtained on calibration stars and resolved late-type giants. Optical modeling of the array and dedicated laboratory measures allowed us to confirm the good accuracy obtained on the calibrated polarized visibilities and closure phases. However, no evidences for polarimetric features at high angular resolution have been detected. The simulations and the results presented here open several perspectives for polar-interferometry, especially in the context of fibered, single-mode combiners.

Some blood chemistry values for five Chesapeake Bay area fishes

USGS Publications Warehouse

Hunn, J.B.; Robinson, P.F.

1966-01-01

Blood samples from gizzard shad,largemouth bass, white perch, pumpkinseed, and toadfish were analyzed for hemoglobin, total plasma protein, total plasma cholesterol, and ion concentrations of plasma sodium, potassium, and chloride. The hemoglobin concentration and total plasma cholesterol found in a given species seem to have positive correlation with the customary activity level of that species. The plasma ionic concentrations in general agree with those found by other authors.

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.

Ion distribution in quaternary-ammonium-functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion-exchange membranes.

PubMed

Weiber, E Annika; Jannasch, Patric

2014-09-01

A series of copoly(arylene ether sulfone)s that have precisely two, three, or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion-exchange membranes. The copolymers are synthesized by condensation polymerizations that involve either di-, tri-, or tetramethylhydroquinone followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small-angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ion-exchange capacity (IEC) of 2.1 meq g(-1), the water uptake decreases with the increasing local density of QA groups. Moreover, at moderate IECs at 20 °C, the Br(-) conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, the location of multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with a high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

Chemical vapor deposition of gallium nitride from the GaCl(3)+NH(3) system. Theoretical study of the structure and thermodynamics of potential intermediates formed in the gaseous phase.

PubMed

Kovács, Attila

2002-06-17

Quantum chemical calculations at the B3P86/6-311G(d,p) level have been performed on potential intermediate molecules in the chemical vapor deposition (CVD) of GaN from the GaCl(3) + NH(3) system. The investigated molecules included the monomer (Cl(x)GaNH(x), x = 1-3) and oligomer species (Cl(2)GaNH(2))(n) with n = 1-3 and (ClGaNH)(n) with n = 1-4 as well as the respective chain dimers and trimers. The calculations revealed the importance of intramolecular Cl...H hydrogen bonding and dipole-dipole interactions in determining the conformational properties of the larger species. Except for the ClGaNH monomer, the Ga[bond]N bonding has a single bond character with a strong ionic contribution. Our thermodynamic study of the composition of the gaseous phase supported the predominance of the Cl(3)GaNH(3) complex under equilibrium conditions. Additionally, the calculated Gibbs free energies of various GaCl(3) + NH(3) reactions imply the favored formation of "saturated" chain and cyclic oligomers below 1000 K.

SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

NASA Technical Reports Server (NTRS)

Thompson, R. A.

1994-01-01

Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the diskettes are compressed using the PKWARE archiving tools. The utility to unarchive the files, PKUNZIP.EXE, is included. This program was last updated in 1991. SUN and SunOS are registered trademarks of Sun Microsystems, Inc.

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

NASA Astrophysics Data System (ADS)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering capacity to previously studied non-halophilic bacteria. The titration data were used to determine the number of types, concentrations, and associated deprotonation constants of functional groups on the bacterial surface; the neptunium adsorption measurements were used to constrain binding constant values for the important neptunium (V)-bacterial surface species. Together, these results can be incorporated into geochemical speciation models to aid in the prediction of neptunium (V) mobility in complex bacteria-bearing geochemical systems.

Enhanced nonlinear optical responses in donor-acceptor ionic complexes via photo induced energy transfer.

PubMed

Mamidala, Venkatesh; Polavarapu, Lakshminarayana; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua; Ji, Wei

2010-12-06

By complexion of donor and acceptor using ionic interactions, the enhanced nonlinear optical responses of donor-acceptor ionic complexes in aqueous solution were studied with 7-ns laser pulses at 532 nm. The optical limiting performance of negatively charged gold nanoparticles or graphene oxide (Acceptor) was shown to be improved significantly when they were mixed with water-soluble, positively-charged porphyrin (Donor) derivative. In contrast, no enhancement was observed when mixing with negatively-charged porphyrin. Transient absorption studies of the donor-acceptor complexes confirmed that the addition of energy transfer pathway were responsible for excited-state deactivation, which results in the observed enhancement. Fluence, angle-dependent scattering and time correlated single photon counting measurements suggested that the enhanced nonlinear scattering due to faster nonradiative decay should play a major role in the enhanced optical limiting responses.

Magnetic graphene oxide modified by imidazole-based ionic liquids for the magnetic-based solid-phase extraction of polysaccharides from brown alga.

PubMed

Wang, Xiaoqin; Li, Guizhen; Row, Kyung Ho

2017-08-01

Magnetic graphene oxide was modified by four imidazole-based ionic liquids to synthesize materials for the extraction of polysaccharides by magnetic solid-phase extraction. Fucoidan and laminarin were chosen as the representative polysaccharides owing to their excellent pharmaceutical value and availability. Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, and thermogravimetric analysis were applied to characterize the synthesized materials. Single-factor experiments showed that the extraction efficiency of polysaccharides was affected by the amount of ionic liquids for modification, solid-liquid ratio of brown alga and ethanol, the stirring time of brown alga and ionic liquid-modified magnetic graphene oxide materials, and amount of 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide materials added to the brown alga sample solution. The results indicated that 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide possessed better extraction ability than graphene oxide, magnetic graphene oxide, and other three ionic-liquid-modified magnetic graphene oxide materials. The highest extraction recoveries of fucoidan and laminarin extracted by 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide were 93.3 and 87.2%, respectively. In addition, solid materials could be separated and reused easily owing to their magnetic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of Cellulose Chains with Ionic Liquids and Water via MD simulations

NASA Astrophysics Data System (ADS)

Ismail, Ahmed; Rabideau, Brooks

2012-02-01

One promising route for combustible fuel sources which are both renewable and have a low environmental impact is the conversion of waste biomass into tailor-made fuels. An important aspect of this process is the low-energy separation of cellulose from the biomass. Ionic liquids (ILs) have proven to be very good in dissolving cellulose with the added benefit of being essentially non-volatile making them ideal for ``green'' processing. IL research, however, remains relatively new, with many parts of this dissolution process remaining uncertain. We examine the behavior of cellulose with the ionic liquids [BMIM]Cl, [EMIM]Ac and [DMIM]DMP as well as water via MD simulation. All three ionic liquids have been observed to dissolve cellulose quite well yet have differently sized anions. We explore these differences and the impacts they have on their interactions with cellulose. First we examine the dynamics of a single cellulose strand in these ionic liquids. We determine the radius of gyration and the hydrogen bonds that are formed between the anions and cellulose. Next, we probe the dissolution mechanism of multiple, bound cellulose strands examining of multiple, bound cellulose strands examining interactions at the IL/cellulose interface and the breakup of inter-cellulose hydrogen bonds.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Coulombic interactions during advection-dominated transport of ions in porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Stolze, Lucien; Rolle, Massimo

2017-04-01

Solute transport of charged species in porous media is significantly affected by the electrochemical migration term resulting from the charge-induced interactions among dissolved ions and with solid surfaces. Therefore, the characterization of such Coulombic interactions and their effect on multicomponent ionic transport is of critical importance for assessing the fate of charged solutes in porous media. In this work we present a detailed investigation of the electrochemical effects during conservative multicomponent ionic transport in homogeneous and heterogeneous domains by means of laboratory bench-scale experiments and numerical simulations. The investigation aims at quantifying the key role of small-scale electrostatic interactions in flow-through systems, especially when advection is the dominant mass-transfer process. Considering dilute solutions of strong electrolytes (e.g., MgCl2 and NaBr) we report results showing the important role of Coulombic interactions in the lateral displacement of the different ionic species for steady-state transport scenarios in which the solutions are continuously injected through different portions of the flow-through chamber [1, 2]. Successively, we focus our attention on transient transport and pulse injection of the electrolytes. In these experiments high-resolution spatial and temporal monitoring of the ions' concentrations (600 samples; 1800 concentration measurements), at closely spaced outlet ports (5 mm), allowed us resolving the effects of charge interactions on the temporal breakthrough and spatial profiles of the cations and anions [3]. The interpretation of the experimental results requires a multicomponent modeling approach with an accurate description of local hydrodynamic dispersion, as well as the explicit quantification of the dispersive fluxes' cross-coupling due to the Coulombic interactions between the charged species. A new 2-D simulator [4], coupling the solution of the multicomponent ionic transport problem with the geochemical code PHREEQC has been developed and used to quantitatively interpret the experimental results. References [1] Rolle M., Muniruzzaman M., Haberer C.M. and P. Grathwohl (2013). Geochim. Cosmochim. Acta 120, 195-205. [2] Muniruzzaman M., Haberer C.M., Grathwohl P. and M. Rolle (2014). Geochim. Cosmochim. Acta 141, 656-669. [3] Muniruzzaman M. and M. Rolle (2017). Water Resour. Res. (in press). [4] Muniruzzaman M. and M. Rolle (2016). Adv. Water Resour. 98, 1-15.

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

PubMed Central

Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-01-01

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid

NASA Astrophysics Data System (ADS)

Wu, Fei; Xu, Changhui; Margulis, Claudio J.

2018-05-01

In a set of recent publications [C. J. Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011); C. H. Xu et al., J. Am. Chem. Soc. 135, 17528 (2013); C. H. Xu and C. J. Margulis, J. Phys. Chem. B 119, 532 (2015); and K. B. Dhungana et al., J. Phys. Chem. B 121, 8809 (2017)], we explored for selected ionic liquids the early stages of excess charge localization and reactivity relevant both to electrochemical and radiation chemistry processes. In particular, Xu and Margulis [J. Phys. Chem. B 119, 532 (2015)] explored the dynamics of an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. When electrons are produced from an ionic liquid, the more elusive hole species are also generated. Depending on the nature of cations and anions and the relative alignment of their electronic states in the condensed phase, the very early hole species can nominally be neutral radicals—if the electron is generated from anions—or doubly charged radical cations if their origin is from cations. However, in reality early excess charge localization is more complex and often involves more than one ion. The dynamics and the transient spectroscopy of the hole are the main objects of this study. We find that in the case of 1-methyl-1-butyl-pyrrolidinium dicyanamide, it is the anions that can most easily lose an electron becoming radical species, and that hole localization is mostly on anionic nitrogen. We also find that the driving force for localization of an excess hole appears to be smaller than that for an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. The early transient hole species can absorb light in the visible, ultraviolet, and near infrared regions, and we are able to identify the type of states being connected by these transitions.

New molten salt systems for high temperature molten salt batteries: Ternary and quaternary molten salt systems based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

Using a new simulative technique developed by us, we systematically investigated new ternary or quaternary molten salt systems, which are based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr binary systems, for use as electrolytes in thermal batteries, and evaluated their ionic conductivities and melting points experimentally. It was confirmed experimentally that LiF-LiBr-KF (melting point: 425 °C, ionic conductivity at 500 °C: 2.52 S cm -1), LiCl-LiBr-KF (405 °C, 2.56 S cm -1), LiCl-LiBr-NaF-KF (425 °C, 3.11 S cm -1), LiCl-LiBr-NaCl-KCl (420 °C, 2.73 S cm -1), and LiCl-LiBr-NaBr-KBr (420 °C, 2.76 S cm -1) meet our targets for both melting point (350-430 °C) and ionic conductivity (2.0 S cm -1 and higher at 500 °C). A single cell using the newly developed LiCl-LiBr-NaCl-KCl molten salt as an electrolyte was prepared, and the DC-IR of the cell decreased by 20% than that of a single cell using the conventional LiCl-KCl molten salt. It was therefore concluded that the use of new quaternary molten salt systems can improve the discharge rate-capability in practical battery applications because of their high ionic conductivities.

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.

Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

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

Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.

2015-09-28

We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means ofmore » their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2+} cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected.« less

Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

PubMed

Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

2017-07-01

Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

2018-05-01

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

Capillary electrophoresis application in metal speciation and complexation characterization

USDA-ARS?s Scientific Manuscript database

Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

ADSORPTION MECHANISMS AND TRANSPORT BEHAVIOR BETWEEN SELENATE AND SELENITE ON DIFFERENT SORBENTS

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

Snyder, Michelle MV; Um, Wooyong

Adsorption of different oxidation species of selenium (Se), selenate (SeO42-) and selenite (SeO32-), with varying pHs (2 - 10) and ionic strengths (I = 0.01 M, 0.1 M and 1.0 M NaNO3) was measured on quartz, aluminum oxide, and synthetic iron oxide (ferrihydrite) using batch reactors to obtain a more detailed understanding of the adsorption mechanisms (e.g., inner- and outer-sphere complex). In addition to the batch experiments with single minerals contained in native Hanford Site sediment, additional batch adsorption studies were conducted with native Hanford Site sediment and groundwater as a function of 1) total Se concentration (from 0.01 tomore » 10 mg L-1) and 2) soil to solution ratios (1:20 and 1:2 grams per mL). Results from these batch studies were compared to a set of saturated column experiments that were conducted with natural Hanford sediment and groundwater spiked with either selenite or selenate to observe the transport behavior of these species. Both batch and column results indicated that selenite adsorption was consistently higher than that of selenate in all experimental conditions used. These different adsorption mechanisms between selenite and selenate result in the varying mobility of Se in the subsurface environment and explain the dependence on the oxidation species.« less

First examples of organosilica-based ionogels: synthesis and electrochemical behavior

PubMed Central

Löbbicke, Ruben; Kirchner, Barbara; Leroux, Fabrice

2017-01-01

The article describes the synthesis and properties of new ionogels for ion transport. A new preparation process using an organic linker, bis(3-(trimethoxysilyl)propyl)amine (BTMSPA), yields stable organosilica matrix materials. The second ionogel component, the ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium 4-methylbenzenesulfonate, [BmimSO3H][PTS], can easily be prepared with near-quantitative yields. [BmimSO3H][PTS] is the proton conducting species in the ionogel. By combining the stable organosilica matrix with the sulfonated ionic liquid, mechanically stable, and highly conductive ionogels with application potential in sensors or fuel cells can be prepared. PMID:28487817

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Changes in the quaternary structure of phosphoenolpyruvate carboxylase induced by ionic strength affect its catalytic activity.

PubMed

Wagner, R; Gonzalez, D H; Podesta, F E; Andreo, C S

1987-05-04

Phosphoenolpyruvate carboxylase from maize leaves dissociated into dimers and/or monomers when exposed to increasing ionic strength (e.g. 200-400 mM NaCl) as indicated by gel filtration experiments. Changes in the oligomerization state were dependent on pH, time of preincubation with salt and protein concentration. A dissociation into dimers and monomers was observed at pH 8, while at pH 7 dissociation into the dimeric form only was observed. Exposure of the enzyme to higher ionic strength decreased the activity in a time-dependent manner. Turnover conditions and glucose 6-phosphate protected the carboxylase from the decay in activity, which was faster at pH 7 than at pH 8. The results suggest that changes in activity of the enzyme, following exposure to high ionic strength, are the consequence of dissociation. Tetrameric and dimeric forms of the phosphoenolpyruvate carboxylase seemingly reveal different catalytic properties. We suggest that the distinct catalytic properties of the different oligomeric species of phosphoenolpyruvate carboxylase and changes in the equilibrium between them could be the molecular basis for an effective regulation of metabolite levels by this key enzyme of C4 plants.

Spatial inhomogeneities in ionic liquids, charged proteins, and charge stabilized colloids from collective variables theory.

PubMed

Patsahan, O; Ciach, A

2012-09-01

Effects of size and charge asymmetry between oppositely charged ions or particles on spatial inhomogeneities are studied for a large range of charge and size ratios. We perform a stability analysis of the primitive model of ionic systems with respect to periodic ordering using the collective variables-based theory. We extend previous studies [Ciach et al., Phys. Rev. E 75, 051505 (2007)] in several ways. First, we employ a nonlocal approximation for the reference hard-sphere fluid which leads to the Percus-Yevick pair direct correlation functions for the uniform case. Second, we use the Weeks-Chandler-Anderson regularization scheme for the Coulomb potential inside the hard core. We determine the relevant order parameter connected with the periodic ordering and analyze the character of the dominant fluctuations along the λ lines. We show that the above-mentioned modifications produce large quantitative and partly qualitative changes in the phase diagrams obtained previously. We discuss possible scenarios of the periodic ordering for the whole range of size and charge ratios of the two ionic species, covering electrolytes, ionic liquids, charged globular proteins or nanoparticles in aqueous solutions, and charge-stabilized colloids.

Understanding the impact of ionic liquid pretreatment on eucalyptus

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

Centikol, Ozgul; Dibble, Dean; Cheng, Gang

2010-01-01

The development of cost-competitive biofuels necessitates the realization of advanced biomass pretreatment technologies. Ionic liquids provide a basis for one of the most promising pretreatment technologies and are known to allow effective processing of cellulose and some biomass species. Here, we demonstrate that the ionic liquid 1-ethyl-3-methyl imidazolium acetate, [C2mim][OAc], induces structural changes at the molecular level in the cell wall of Eucalyptus globulus. Deacetylation of xylan, acetylation of the lignin units, selective removal of guaiacyl units (increasing the syringyl:guaiacyl ratio) and decreased {beta}-ether content were the most prominent changes observed. Scanning electron microscopy images of the plant cell wallmore » sections reveal extensive swelling during [C2mim][OAc] pretreatment. X-ray diffraction measurements indicate a change in cellulose crystal structure from cellulose I to cellulose II after [C2mim][OAc] pretreatment. Enzymatic saccharification of the pretreated material produced increased sugar yields and improved hydrolysis kinetics after [C2mim][OAc] pretreatment. These results provide new insight into the mechanism of ionic liquid pretreatment and reaffirm that this approach may be promising for the production of cellulosic biofuels from woody biomass.« less

Influence of the anion nature and alkyl substituents in the behavior of ionic liquids derived from phenylpyridines

NASA Astrophysics Data System (ADS)

Dreyse, Paulina; Alarcón, Antonia; Galdámez, Antonio; González, Iván; Cortés-Arriagada, Diego; Castillo, Francisco; Mella, Andy

2018-02-01

Quaternary alkyl 2-phenylpyridinium and 2-(2,4-difluorophenyl)pyridinium amines with iodide, hexafluorophosphate and bis(trifluoromethylsulfonyl)imide anions have been fully characterized by 1H NMR, FT-IR and MALDI mass spectroscopic methods and studied by quantum chemistry calculations. The compounds with bis(trifluoromethylsulfonyl)imide anion can be classified as ionic liquids, because they melt at room temperature. The quaternary amines with iodide and hexafluorophosphate anions are solid at 25 °C. The X-ray diffraction characterization of the 2-(2,4-difluorophenyl)-1-methylphenylpyridinium hexafluorophosphate and 1-ethyl-2-(2,4-difluorophenyl)phenylpyridinium hexafluorophosphate show an extensive series of Csbnd H⋯F, Csbnd F⋯π and Psbnd F⋯π intermolecular interactions, which give rise to a supramolecular network. The relationship between the solid-state structures and the melting points is discussed by the evaluation of the thermal behavior based on experimental data from Differential Scanning Calorimetry (DSC) studies, and also using the analysis of the ion pairs binding energies. These new compounds based on phenylpyridine allow us to grow the diversity of ionic liquids and their crystalline salts, increasing the knowledge about the chemical and physical properties of these ionic species.

Thermal and energetic processing of astrophysical ice analogues rich in SO2

NASA Astrophysics Data System (ADS)

Kaňuchová, Z.; Boduch, Ph.; Domaracka, A.; Palumbo, M. E.; Rothard, H.; Strazzulla, G.

2017-08-01

Context. Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the solar system. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (I.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Aims: Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. Methods: We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment (30 keV He+) of the same mixtures. We used in situ Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results: The results indicate that ionic species such as HSO, HSO, and S2O are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions: The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets.

Electrokinetics Models for Micro and Nano Fluidic Impedance Sensors

DTIC Science & Technology

2010-11-01

primitive Differential-Algebraic Equations (DAEs), used to process and interpret the experimentally measured electrical impedance data (Sun and Morgan...field, and species respectively. A second-order scheme was used to calculate the ionic species distribution. The linearized algebraic equations were...is governed by the Poisson equation 2 0 0 r i i i F z cε ε φ∇ + =∑ where ε0 and εr are, respectively, the electrical permittivity in the vacuum

Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.

PubMed

Chambreau, Steven D; Koh, Christine J; Popolan-Vaida, Denisia M; Gallegos, Christopher J; Hooper, Justin B; Bedrov, Dmitry; Vaghjiani, Ghanshyam L; Leone, Stephen R

2016-10-07

The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIM + DCA - ) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Reaction product formation at m/z 42, 43, 44, 67, 85, 126, and higher masses was observed as a function of HNO 3 exposure. The identities of the product species were assigned to the masses on the basis of their ionization energies. The observed exposure profile of the m/z 67 signal suggests that the excess gaseous HNO 3 initiates rapid reactions near the surface of the RTIL aerosol. Nonreactive molecular dynamics simulations support this observation, suggesting that diffusion within the particle may be a limiting step. The mechanism is consistent with previous reports that nitric acid forms protonated dicyanamide species in the first step of the reaction.

Nonlinear Porous Diffusion Modeling of Hydrophilic Ionic Agrochemicals in Astomatous Plant Cuticle Aqueous Pores: A Mechanistic Approach.

PubMed

Tredenick, Eloise C; Farrell, Troy W; Forster, W Alison; Psaltis, Steven T P

2017-01-01

The agricultural industry requires improved efficacy of sprays being applied to crops and weeds in order to reduce their environmental impact and deliver improved financial returns. Enhanced foliar uptake is one means of improving efficacy. The plant leaf cuticle is known to be the main barrier to diffusion of agrochemicals within the leaf. The usefulness of a mathematical model to simulate uptake of agrochemicals in plant cuticles has been noted previously in the literature, as the results of each uptake experiment are specific to each formulation of active ingredient, plant species and environmental conditions. In this work we develop a mathematical model and numerical simulation for the uptake of hydrophilic ionic agrochemicals through aqueous pores in plant cuticles. We propose a novel, nonlinear, porous diffusion model for ionic agrochemicals in isolated cuticles, which extends simple diffusion through the incorporation of parameters capable of simulating: plant species variations, evaporation of surface droplet solutions, ion binding effects on the cuticle surface and swelling of the aqueous pores with water. We validate our theoretical results against appropriate experimental data, discuss the key sensitivities in the model and relate theoretical predictions to appropriate physical mechanisms. Major influencing factors have been found to be cuticle structure, including tortuosity and density of the aqueous pores, and to a lesser extent humidity and cuticle surface ion binding effects.

Nonlinear Porous Diffusion Modeling of Hydrophilic Ionic Agrochemicals in Astomatous Plant Cuticle Aqueous Pores: A Mechanistic Approach

PubMed Central

Tredenick, Eloise C.; Farrell, Troy W.; Forster, W. Alison; Psaltis, Steven T. P.

2017-01-01

The agricultural industry requires improved efficacy of sprays being applied to crops and weeds in order to reduce their environmental impact and deliver improved financial returns. Enhanced foliar uptake is one means of improving efficacy. The plant leaf cuticle is known to be the main barrier to diffusion of agrochemicals within the leaf. The usefulness of a mathematical model to simulate uptake of agrochemicals in plant cuticles has been noted previously in the literature, as the results of each uptake experiment are specific to each formulation of active ingredient, plant species and environmental conditions. In this work we develop a mathematical model and numerical simulation for the uptake of hydrophilic ionic agrochemicals through aqueous pores in plant cuticles. We propose a novel, nonlinear, porous diffusion model for ionic agrochemicals in isolated cuticles, which extends simple diffusion through the incorporation of parameters capable of simulating: plant species variations, evaporation of surface droplet solutions, ion binding effects on the cuticle surface and swelling of the aqueous pores with water. We validate our theoretical results against appropriate experimental data, discuss the key sensitivities in the model and relate theoretical predictions to appropriate physical mechanisms. Major influencing factors have been found to be cuticle structure, including tortuosity and density of the aqueous pores, and to a lesser extent humidity and cuticle surface ion binding effects. PMID:28539930

Theoretical and experimental studies of water interaction in acetate based ionic liquids.

PubMed

Shi, Wei; Damodaran, Krishnan; Nulwala, Hunaid B; Luebke, David R

2012-12-05

Water interactions in 1-ethyl-3-methylimidazolium acetate ([emim][CH(3)COO]) were studied utilizing classical and ab initio simulation methods. The self-diffusivities for water and the ionic liquid (IL) were studied experimentally using pulse field gradient NMR spectroscopy and correlated with computational results. Water forms hydrogen bonding networks with the ionic liquid, and depending on the concentration of water, there are profound effects on the self-diffusivities of the various species. Both simulation and experiments show that the self-diffusivities for species in the water-[emim][CH(3)COO] system exhibit minima at 40-50 mol% water. Water interaction with the [CH(3)COO](-) anion predominates over the water-water and water-cation interactions at most water concentrations. Simulations further indicate that decreasing water-[CH(3)COO](-) interaction will increase the IL and water self-diffusivities. Self-diffusivities in the water-IL systems are dependent upon the cation in a complex way. Water interactions with [P(4444)][CH(3)COO] are reduced compared to [emim][CH(3)COO]. The [P(4444)](+) cation is bulkier than the [emim](+) cation and has a smaller self-diffusivity, but when water was introduced to [P(4444)] [CH(3)COO], the water-[CH(3)COO](-) hydrogen bonding network in the [P(4444)][CH(3)COO] was much smaller than the one observed in [emim][CH(3)COO].

Specific binding of (/sup 3/H-Tyr8)physalaemin to rat submaxillary gland substance P receptor

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

Bahouth, S.W.; Lazaro, D.M.; Brundish, D.E.

1985-01-01

(/sup 3/H)Physalaemin ((/sup 3/H)PHY) binds to a single class of noninteracting sites on rat submaxillary gland membranes suspended in high ionic strength media with a KD of 2.7 nM, a Bmax of 240 fmol/mg of protein, and low nonspecific binding. The relative potencies of substance P (SP) and its fragments in competing with (/sup 3/H)PHY correlate with their relative salivation potencies. This indicates that (/sup 3/H)PHY interacts with a physiologically relevant SP receptor. In low ionic strength media, the KD of (/sup 3/H)PHY does not change, but SP and some of its fragments are more potent than PHY in competingmore » with (/sup 3/H) PHY. Computer-assisted analysis of (/sup 3/H)PHY and (/sup 3/H)SP binding in high and low ionic strength media demonstrated that both peptides are equipotent in high ionic strength but that the affinity of SP increases by 70-fold in low ionic strength. The SP fragments that contain a basic residue in positions 1 and/or 3 also display an increased affinity in low ionic strength. These findings document that (/sup 3/H)PHY binding in high ionic strength (mu . 0.6) accurately reflects the pharmacological potencies of agonists on the SP-P receptor. The binding of (/sup 3/H)PHY, like that of (/sup 3/H)SP, increases by the addition of divalent cations (Mg2+ greater than Ca2+ greater than Mn2+). Guanine nucleotides decrease (/sup 3/H)PHY binding by decreasing the Bmax to the same level (160 fmol/mg of protein), in the presence or absence of Mg2+.« less

Effects of rare earth ionic doping on microstructures and electrical properties of CaCu{sub 3}Ti{sub 4}O{sub 12} ceramics

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

Xue, Renzhong; Department of Technology and Physics, Zhengzhou University of Light Industry, Zhengzhou 450002; Chen, Zhenping, E-mail: xrzbotao@163.com

2015-06-15

Graphical abstract: The dielectric constant decreases monotonically with reduced RE doping ion radius and is more frequency independent compared with that of pure CCTO sample. - Highlights: • The mean grain sizes decrease monotonically with reduced RE doping ionic radius. • Doping gives rise to the monotonic decrease of ϵ{sub r} with reduced RE ionic radius. • The nonlinear coefficient and breakdown field increase with RE ionic doping. • α of all the samples is associated with the potential barrier width rather than Φ{sub b}. - Abstract: Ca{sub 1–x}R{sub x}Cu{sub 3}Ti{sub 4}O{sub 12}(R = La, Nd, Eu, Gd, Er; xmore » = 0 and 0.005) ceramics were prepared by the conventional solid-state method. The influences of rare earth (RE) ion doping on the microstructure, dielectric and electrical properties of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) ceramics were investigated systematically. Single-phase formation is confirmed by XRD analyses. The mean grain size decreases monotonically with reduced RE ion radius. The EDS results reveal that RE ionic doping reduces Cu-rich phase segregation at the grain boundaries (GBs). Doping gives rise to the monotonic decrease of dielectric constant with reduced RE ionic radius but significantly improves stability with frequency. The lower dielectric loss of doped samples is obtained due to the increase of GB resistance. In addition, the nonlinear coefficient and breakdown field increase with RE ionic doping. Both the fine grains and the enhancement of potential barrier at GBs are responsible for the improvement of the nonlinear current–voltage properties in doped CCTO samples.« less

Super Dielectric Materials

PubMed Central

Fromille, Samuel; Phillips, Jonathan

2014-01-01

Evidence is provided here that a class of materials with dielectric constants greater than 105 at low frequency (<10−2 Hz), herein called super dielectric materials (SDM), can be generated readily from common, inexpensive materials. Specifically it is demonstrated that high surface area alumina powders, loaded to the incipient wetness point with a solution of boric acid dissolved in water, have dielectric constants, near 0 Hz, greater than 4 × 108 in all cases, a remarkable increase over the best dielectric constants previously measured for energy storage capabilities, ca. 1 × 104. It is postulated that any porous, electrically insulating material (e.g., high surface area powders of silica, titania, etc.), filled with a liquid containing a high concentration of ionic species will potentially be an SDM. Capacitors created with the first generated SDM dielectrics (alumina with boric acid solution), herein called New Paradigm Super (NPS) capacitors display typical electrostatic capacitive behavior, such as increasing capacitance with decreasing thickness, and can be cycled, but are limited to a maximum effective operating voltage of about 0.8 V. A simple theory is presented: Water containing relatively high concentrations of dissolved ions saturates all, or virtually all, the pores (average diameter 500 Å) of the alumina. In an applied field the positive ionic species migrate to the cathode end, and the negative ions to the anode end of each drop. This creates giant dipoles with high charge, hence leading to high dielectric constant behavior. At about 0.8 V, water begins to break down, creating enough ionic species to “short” the individual water droplets. Potentially NPS capacitor stacks can surpass “supercapacitors” in volumetric energy density. PMID:28788298

Super Dielectric Materials.

PubMed

Fromille, Samuel; Phillips, Jonathan

2014-12-22

Evidence is provided here that a class of materials with dielectric constants greater than 10⁵ at low frequency (<10 -2 Hz), herein called super dielectric materials (SDM), can be generated readily from common, inexpensive materials. Specifically it is demonstrated that high surface area alumina powders, loaded to the incipient wetness point with a solution of boric acid dissolved in water, have dielectric constants, near 0 Hz, greater than 4 × 10⁸ in all cases, a remarkable increase over the best dielectric constants previously measured for energy storage capabilities, ca. 1 × 10⁴. It is postulated that any porous, electrically insulating material (e.g., high surface area powders of silica, titania, etc. ), filled with a liquid containing a high concentration of ionic species will potentially be an SDM. Capacitors created with the first generated SDM dielectrics (alumina with boric acid solution), herein called New Paradigm Super (NPS) capacitors display typical electrostatic capacitive behavior, such as increasing capacitance with decreasing thickness, and can be cycled, but are limited to a maximum effective operating voltage of about 0.8 V. A simple theory is presented: Water containing relatively high concentrations of dissolved ions saturates all, or virtually all, the pores (average diameter 500 Å) of the alumina. In an applied field the positive ionic species migrate to the cathode end, and the negative ions to the anode end of each drop. This creates giant dipoles with high charge, hence leading to high dielectric constant behavior. At about 0.8 V, water begins to break down, creating enough ionic species to "short" the individual water droplets. Potentially NPS capacitor stacks can surpass "supercapacitors" in volumetric energy density.

The smog-fog-smog cycle and acid deposition

NASA Astrophysics Data System (ADS)

Pandis, Spyros N.; Seinfeld, John H.; Pilinis, Christodoulos

1990-10-01

A model including descriptions of aerosol and droplet microphysics, gas and aqueous-phase chemistry, and deposition is used to study the transformation of aerosol to fog droplets and back to aerosol in an urban environment. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium and well as in the total aerosol mass concentration. The sulfate produced during fog episodes favors the aerosol particles that have access to most of the fog liquid water which are usually the large particles. Aerosol scavenging efficiencies of around 80 percent are calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition and can introduce errors in the reported values of the ionic species deposition velocities. Differences in the major ionic species deposition velocities can be explained by their distribution over the droplet size spectrum and can be correlated with the species average diameter. Two different expressions are derived for use in fog models for the calculation of the liquid water deposition velocity during fog growth and dissipation stages.

The adsorption, stability and properties of Mn6Cr Single-Molecule-Magnets studied by means of nc-AFM, STM, XAS and Spin-resolved Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Heinzmann, U.; Gryzia, A.; Helmstedt, A.; Dohmeier, N.; Predatsch, H.; Brechling, A.; Müller, N.; Sacher, M.; Hoeke, V.; Krickemeyer, E.; Glaser, T.; Bouvron, S.; Fonin, M.; Neumann, M.

2012-11-01

The ionic single-molecule-magnet [MnIII6CrIII]3 with corresponding three counterions has been deposited on different surfaces and studied with respect to its structure and its electronic and magnetic properties. This is the first time that spin polarization of photoelectrons ejected by means of circularly polarized synchrotron radiation has been measured in a single-molecule-magnet.

Ions in water: Free energies, surface effects, and geometrical constraints

NASA Astrophysics Data System (ADS)

Herce, Henry David

In this work, we present our results for ion solvation in finite and infinite water clusters. Molecular Dynamic simulations are used to connect the fundamental macroscopic quantities such as free energy, internal energy and entropy with the underlying microscopic description. Molecular dynamics studies complement experimental results and lead to a deeper insight into the solvation and diffusion of ionic species. Beyond its intrinsic interest, the ion solvation problem has practical relevance because of its role as ideal model system with which to construct and test ion-water interaction potentials. The ionic charging free energy is a very sensitive probe for the treatment of electrostatics in any given simulation setting. In this work, we present methods to compute the ionic charging free energy in systems characterized by atomic charges, and higher-order multipoles, mainly dipoles and quadrupoles. The results of these methods under periodic boundary conditions and spherical boundary conditions are then compared. For the treatment of spherical boundary conditions, we introduce a generalization of Gauss' law that links the microscopic variables to the relevant thermodynamic quantities. Ionic solvation in finite clusters is a problem relevant for many areas of chemistry and biology, such as the gas-liquid interface of tropospheric aerosol particles, or the interphase between water and proteins, membranes, etc. Careful evaluations of the free energy, internal energy and entropy are used to address controversial or unresolved issues, related to the underlying physical cause of surface solvation, and the basic assumptions that go with it. Our main conclusions are the following: (i) The main cause of surface solvation of a single ion in a water cluster is both water and ion polarization, coupled to the charge and size of the ion. Interestingly, the total energy of the ion increases near the cluster surface, while the total energy of water decreases. Also, our analysis clearly shows that the cause of surface solvation is not the size of the total water dipole (unless this is too small). (ii) The entropic contribution is the same order of magnitude as the energetic contribution, and therefore cannot be neglected for quantitative results. (iii) A pure energetic analysis can give a qualitative description of the ion position at room temperature. (iv) We have observed surface solvation of a large positive iodine-like ion in a polarizable water cluster, but not in a non-polarizable water cluster.

Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

NASA Astrophysics Data System (ADS)

Das, S.; Ghosh, A.

2016-06-01

In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

Ionomers for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph

For ionic actuators and battery separators, it is vital to utilize single-ion conducting ionomers that avoid the detrimental polarization of other ions. Single-ion conducting ionomers are synthesized based on DFT calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for battery separators that conduct Li+ or Na+. Characterization by X-ray scattering, dielectric spectroscopy, FTIR, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. 7Li NMR diffusion measurements find that diffusion is faster than expected by conductivity using the Nernst-Einstein equation, which means that the majority of Li diffusion occurs by ion pairs moving with the polymer segmental motion. Segmental motion only contributes to ionic conduction in the rare event that one of these ion pairs has an extra Li (a positive triple ion). This leads us to a new metric for ion-conducting soft materials, the product of the cation number density p0 and their diffusion coefficient D; p0D is the diffusive flux of lithium ions. This new metric has a maximum at intermediate ion content that corresponds to the overlap of ion pair polarizability volumes. At higher ion contents, the ion pairs interact strongly and form larger aggregation states that retard segmental motion of both mobile ion pairs and triple ions.

MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

Polarizable molecular interactions in condensed phase and their equivalent nonpolarizable models.

PubMed

Leontyev, Igor V; Stuchebrukhov, Alexei A

2014-07-07

Earlier, using phenomenological approach, we showed that in some cases polarizable models of condensed phase systems can be reduced to nonpolarizable equivalent models with scaled charges. Examples of such systems include ionic liquids, TIPnP-type models of water, protein force fields, and others, where interactions and dynamics of inherently polarizable species can be accurately described by nonpolarizable models. To describe electrostatic interactions, the effective charges of simple ionic liquids are obtained by scaling the actual charges of ions by a factor of 1/√(ε(el)), which is due to electronic polarization screening effect; the scaling factor of neutral species is more complicated. Here, using several theoretical models, we examine how exactly the scaling factors appear in theory, and how, and under what conditions, polarizable Hamiltonians are reduced to nonpolarizable ones. These models allow one to trace the origin of the scaling factors, determine their values, and obtain important insights on the nature of polarizable interactions in condensed matter systems.

Nonlinear ionic transport through microstructured solid electrolytes: homogenization estimates

NASA Astrophysics Data System (ADS)

Curto Sillamoni, Ignacio J.; Idiart, Martín I.

2016-10-01

We consider the transport of multiple ionic species by diffusion and migration through microstructured solid electrolytes in the presence of strong electric fields. The assumed constitutive relations for the constituent phases follow from convex energy and dissipation potentials which guarantee thermodynamic consistency. The effective response is heuristically deduced from a multi-scale convergence analysis of the relevant field equations. The resulting homogenized response involves an effective dissipation potential per species. Each potential is mathematically akin to that of a standard nonlinear heterogeneous conductor. A ‘linear-comparison’ homogenization technique is then used to generate estimates for these nonlinear potentials in terms of available estimates for corresponding linear conductors. By way of example, use is made of the Maxwell-Garnett and effective-medium linear approximations to generate estimates for two-phase systems with power-law dissipation. Explicit formulas are given for some limiting cases. In the case of threshold-type behavior, the estimates exhibit non-analytical dilute limits and seem to be consistent with fields localized in low energy paths.

Ion-size dependent electroosmosis of viscoelastic fluids in microfluidic channels with interfacial slip

NASA Astrophysics Data System (ADS)

Mukherjee, Siddhartha; Goswami, Prakash; Dhar, Jayabrata; Dasgupta, Sunando; Chakraborty, Suman

2017-07-01

We report a study on the ion-size dependent electroosmosis of viscoelastic fluids in microfluidic channels with interfacial slip. Here, we derive an analytical solution for the potential distribution in a parallel plate microchannel, where the effects of finite sized ionic species are taken into account by invoking the free energy formalism. Following this, a purely electroosmotic flow of a simplified Phan-Thien-Tanner (sPTT) fluid is considered. For the sPTT model, linear, quadratic, and exponential kernels are chosen for the stress coefficient function describing its viscoelastic nature across various ranges of Deborah number. The theoretical framework presented in our analysis has been successfully compared with experimental results available in the literature. We believe that the implications of the considered effects on the net volumetric throughput will not only provide a deeper theoretical insight to interpret the electrokinetic data in the presence of ionic species but also serve as a fundamental design tool for novel electrokinetically driven lab-on-a-chip biofluidic devices.

Structure and reactivity of a mononuclear gold(II) complex

NASA Astrophysics Data System (ADS)

Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

2017-12-01

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

Rheological properties of concentrated solutions of gelatin in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate.

PubMed

Horinaka, Jun-Ichi; Okamoto, Arisa; Takigawa, Toshikazu

2016-10-01

Rheological properties of gelatin solutions were examined in concentrated regions. Gelatin species from porcine skin and from bovine bone were dissolved in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate. The dynamic viscoelasticity data for the solutions exhibited rubbery plateaus, indicating the existence of entanglement coupling between gelatin chains in the solutions. From the analogy with rubber elasticity, assuming that the molecular weight between entanglements (Me) is the average mesh size of the entanglement network, Me for gelatin in the solutions were determined from the heights of the rubbery plateaus. Then the value of Me in the molten state (Me,melt), a material constant reflecting the chemical structure of polymer species, for gelatin was estimated to be 8.7×10(3). Compared to synthetic polyamides whose Me,melt were known, Me,melt for gelatin was significantly larger, which could be explained by the densely repeating amide bonds composing gelatin. Copyright © 2016 Elsevier B.V. All rights reserved.

Monitoring of oxidation steps of ascorbic acid redox reaction by kinetics-sensitive voltcoulometry in unsupported and supported aqueous solutions and real samples.

PubMed

Orlický, Jozef; Gmucová, Katarína; Thurzo, Ilja; Pavlásek, Juraj

2003-04-01

Aqueous solutions of ascorbic acid in unsupported and supported aqueous solutions and real samples were studied by the kinetics-sensitive double-step voltcoulommetric method with the aim to contribute to a better understanding of its behavior in biological systems. The data obtained from measurements made on analytes prepared in the laboratory, as well as those made on real samples (some commercial orange drinks, flash of the fresh fruits) point to the redox reaction of L-ascorbic acid (L-AH2) being very sensitive to both the presence of dissolved gaseous species (O2, CO2) and the ionic strenght in the analyte. Either the dissolved gaseous species, or the higher ionic strength caused by both the presence of supporting electrolyte and increased total concentration of ascorbic acid, respectively, give birth to the degradation of L-AH2. Naturally, the highest percentage of L-AH2 was spotted in fresh fruit.

High rate capacitive performance of single-walled carbon nanotube aerogels

DOE PAGES

Van Aken, Katherine L.; Pérez, Carlos R.; Oh, Youngseok; ...

2015-05-30

Single-walled carbon nanotube (SWCNT) aerogels produced by critical-point-drying of wet-gel precursors exhibit unique properties, such as high surface-area-to-volume and strength-to-weight ratios. They are free-standing, are binder-free, and can be scaled to thicknesses of more than 1 mm. In this paper, we examine the electric double layer capacitive behavior of these materials using a common room temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI). Electrochemical performance is assessed through galvanostatic cycling, cyclic voltammetry and impedance spectroscopy. Results indicate stable capacitive performance over 10,000 cycles as well as an impressive performance at high charge and discharge rates, due to accessible pore networks andmore » enhanced electronic and ionic conductivities of SWCNT aerogels. Finally, these materials can find applications in mechanically compressible and flexible supercapacitor devices with high power requirements.« less

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

PubMed Central

Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei; Devaux, Didier; Wong, Dominica H. C.; DeSimone, Joseph M.; Balsara, Nitash P.

2016-01-01

Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10−4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li+/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries. PMID:26699512

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

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

Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei

2015-12-22

Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. Here, we have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10 -4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Limore » +/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.« less

Glass electrolyte composition

DOEpatents

Kucera, Gene H.; Roche, Michael F.

1985-01-01

An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na.sub.2 O, ZrO.sub.2, Al.sub.2 O.sub.3 and SiO.sub.2 in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2.times.10.sup.-3 (ohm-cm).sup.-1 at 300.degree. C. and a glass transition temperature in excess of 500.degree. C.

Glass electrolyte composition

DOEpatents

Kucera, G.H.; Roche, M.F.

1985-01-08

An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na/sub 2/O, ZrO/sub 2/, Al/sub 2/O/sub 3/ and SiO/sub 2/ in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2 x 10/sup -3/ (ohm-cm)/sup -1/ at 300/sup 0/C and a glass transition temperature in excess of 500/sup 0/C.

Phytoremediation of Ionic and Methyl Mercury P

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

Meagher, Richard B.

1999-06-01

Our long-term goal is to enable highly productive plant species to extract, resist, detoxify, and/or sequester toxic heavy metal pollutants as an environmentally friendly alternative to physical remediation methods. We have focused this phytoremediation research on soil and water-borne ionic and methylmercury. Mercury pollution is a serious world-wide problem affecting the health of human and wild-life populations. Methylmercury, produced by native bacteria at mercury-contaminated wetland sites, is a particularly serious problem due to its extreme toxicity and efficient biomagnification in the food chain. We engineered several plant species (e.g., Arabidopsis, tobacco, canola, yellow poplar, rice) to express the bacterial genes,more » merB and/or merA, under the control of plant regulatory sequences. These transgenic plants acquired remarkable properties for mercury remediation. (1) Transgenic plants expressing merB (organomercury lyase) extract methylmercury from their growth substrate and degrade it to less toxic ionic mercury. They grow on concentrations of methylmercury that kill normal plants and accumulate low levels of ionic mercury. (2) Transgenic plants expressing merA (mercuric ion reductase) extract and electrochemically reduce toxic, reactive ionic mercury to much less toxic and volatile metallic mercury. This metal transformation is driven by the powerful photosynthetic reducing capacity of higher plants that generates excess NADPH using solar energy. MerA plants grow vigorously on levels of ionic mercury that kill control plants. Plants expressing both merB and merA degrade high levels of methylmercury and volatilize metallic mercury. These properties were shown to be genetically stable for several generations in the two plant species examined. Our work demonstrates that native trees, shrubs, and grasses can be engineered to remediate the most abundant toxic mercury pollutants. Building on these data our working hypothesis for the next grant period is that transgenic plants expressing the bacterial merB and merA genes will (a) remove mercury from polluted soil and water and (b) prevent methylmercury from entering the food chain. Our specific aims center on understanding the mechanisms by which plants process the various forms of mercury and volatilize or transpire mercury vapor. This information will allow us to improve the design of our current phytoremediation strategies. As an alternative to volatilizing mercury, we are using several new genes to construct plants that will hyperaccumulate mercury in above-ground tissues for later harvest. The Department of Energy's Oak Ridge National Laboratory and Brookhaven National Laboratory have sites with significant levels of mercury contamination that could be cleaned by applying the scientific discoveries and new phytoremediation technologies described in this proposal. The knowledge and expertise gained by engineering plants to hyperaccumulate mercury can be applied to the remediation of other heavy metals pollutants (e.g., arsenic, cesium, cadmium, chromium, lead, strontium, technetium, uranium) found at several DOE facilities.« less

Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

NASA Astrophysics Data System (ADS)

Buyukkilic, Salih

Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations with charge-balancing oxygen vacancies. At higher temperatures near 700 °C, maximum enthalpy of formation shifts toward higher dopant concentrations, as a result of defect disordering. This concentration coincides with that of maximum ionic conductivity, extending the correlation seen previously near room temperature. It is also possible to co-dope these systems with Sm and Nd to further enhance ionic conductivity. For doubly doped ceria electrolytes, the solid solution phase of Ce1-xSm0.5xNd0.5xO2-0.5x (0 ≤ x ≤ 0.30) was investigated. It has been shown that for doubly doped ceria, the maximum enthalpy of formation occurs towards higher dopant concentration than that of singly doped counterparts, with less exothermic association enthalpies. These studies provide insight into the structure-composition-property-stability relations and aid in the rational design of the future SOFCs electrolytes.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

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.

Intrinsic electronic defects and multiple-atom processes in the oxidic semiconductor Ga2O3

NASA Astrophysics Data System (ADS)

Schmeißer, Dieter; Henkel, Karsten

2018-04-01

We report on the electronic structure of gallium oxide (Ga2O3) single crystals as studied by resonant photoelectron spectroscopy (resPES). We identify intrinsic electronic defects that are formed by mixed-atomic valence states. We differentiate three coexisting defect states that differ in their electronic correlation energy and their spatial localization lengths. Their relative abundance is described by a fractional ionicity with covalent and ionic bonding contributions. For Ga2O3, our analyses of the resPES data enable us to derive two main aspects: first, experimental access is given to determine the ionicity based on the original concepts of Pauling and Phillips. Second, we report on multi-atomic energy loss processes in the Ga2p core level and X-ray absorption data. The two experimental findings can be explained consistently in the same context of mixed-atomic valence states and intrinsic electronic defects.

A study of single and binary ion plasma expansion into laboratory-generated plasma wakes

NASA Technical Reports Server (NTRS)

Wright, Kenneth Herbert, Jr.

1988-01-01

Plasma expansion into the wake of a large rectangular plate immersed in a collisionless, supersonic plasma was investigated in laboratory experiments. The experimental conditions address both single ion and binary ion plasma flows for the case of a body whose size is large in comparison with the Debye length, when the potential difference between the body and the plasma is relatively small. A new plasma source was developed to generate equi-velocity, binary ion plasma flows, which allows access to new parameter space that have previously been unavailable for laboratory studies. Specifically, the new parameters are the ionic mass ratio and the ionic component density ratio. In a series of experiments, a krypton-neon plasma is employed where the ambient density ratio of neon to krypton is varied more than an order of magnitude. The expansion in both the single ion and binary ion plasma cases is limited to early times, i.e., a few ion plasma periods, by the combination of plasma density, plasma drift speed, and vacuum chamber size, which prevented detailed comparison with self-similar theory.

Quantifying short-lived events in multistate ionic current measurements.

PubMed

Balijepalli, Arvind; Ettedgui, Jessica; Cornio, Andrew T; Robertson, Joseph W F; Cheung, Kin P; Kasianowicz, John J; Vaz, Canute

2014-02-25

We developed a generalized technique to characterize polymer-nanopore interactions via single channel ionic current measurements. Physical interactions between analytes, such as DNA, proteins, or synthetic polymers, and a nanopore cause multiple discrete states in the current. We modeled the transitions of the current to individual states with an equivalent electrical circuit, which allowed us to describe the system response. This enabled the estimation of short-lived states that are presently not characterized by existing analysis techniques. Our approach considerably improves the range and resolution of single-molecule characterization with nanopores. For example, we characterized the residence times of synthetic polymers that are three times shorter than those estimated with existing algorithms. Because the molecule's residence time follows an exponential distribution, we recover nearly 20-fold more events per unit time that can be used for analysis. Furthermore, the measurement range was extended from 11 monomers to as few as 8. Finally, we applied this technique to recover a known sequence of single-stranded DNA from previously published ion channel recordings, identifying discrete current states with subpicoampere resolution.

Density functional theory study of the capacitance of single file ions in a narrow cylinder

DOE PAGES

Kong, Xian; Wu, Jianzhong; Henderson, Douglas

2014-11-14

In this paper, the differential capacitance of a model organic electrolyte in a cylindrical pore that is so narrow that the ions can form only a single file is studied by means of density functional theory (DFT). Kornyshev (2013), has studied this system and found the differential capacitance to have only a double hump shape (the so-called camel shape) whereas other geometries show this behavior only at low ionic concentrations that are typical for aqueous electrolytes. However, his calculation is rather approximate. In this DFT study we find that the double hump shape occurs only at low ionic concentrations. Atmore » high concentrations, the capacitance has only a single hump. Kornyshev considers a metallic cylinder and approximately includes the contributions of electrostatic images. Electrostatic images are not easily incorporated into DFT. In conclusion, images are not considered in this study and the question of whether Kornyshev’s result is due to his approximations or images cannot be answered. Simulations to answer this question are planned.« less

Modulation by K+ Plus NH4+ of microsomal (Na+, K+)-ATPase activity in selected ontogenetic stages of the diadromous river shrimp Macrobrachium amazonicum (Decapoda, Palaemonidae).

PubMed

Leone, Francisco A; Bezerra, Thais M S; Garçon, Daniela P; Lucena, Malson N; Pinto, Marcelo R; Fontes, Carlos F L; McNamara, John C

2014-01-01

We investigate the synergistic stimulation by K(+) plus NH4 (+) of (Na(+), K(+))-ATPase activity in microsomal preparations of whole zoea I and decapodid III, and in juvenile and adult river shrimp gills. Modulation of (Na(+), K(+))-ATPase activity is ontogenetic stage-specific, and particularly distinct between juveniles and adults. Although both gill enzymes exhibit two different sites for K(+) and NH4 (+) binding, in the juvenile enzyme, these two sites are equivalent: binding by both ions results in slightly stimulated activity compared to that of a single ionic species. In the adult enzyme, the sites are not equivalent: when one ion occupies its specific binding site, (Na(+), K(+))-ATPase activity is stimulated synergistically by ≈ 50% on binding of the complementary ion. Immunolocalization reveals the enzyme to be distributed predominantly throughout the intralamellar septum in the gill lamellae of juveniles and adults. Western blot analyses demonstrate a single immunoreactive band, suggesting a single (Na(+), K(+))-ATPase α-subunit isoform that is distributed into different density membrane fractions, independently of ontogenetic stage. We propose a model for the modulation by K(+) and NH4 (+) of gill (Na(+), K(+))-ATPase activity. These findings suggest that the gill enzyme may be regulated by NH4 (+) during ontogenetic development in M. amazonicum.

Modulation By K+ Plus NH4 + of Microsomal (Na+, K+)-ATPase Activity in Selected Ontogenetic Stages of the Diadromous River Shrimp Macrobrachium amazonicum (Decapoda, Palaemonidae)

PubMed Central

Leone, Francisco A.; Bezerra, Thais M. S.; Garçon, Daniela P.; Lucena, Malson N.; Pinto, Marcelo R.; Fontes, Carlos F. L.; McNamara, John C.

2014-01-01

We investigate the synergistic stimulation by K+ plus NH4 + of (Na+, K+)-ATPase activity in microsomal preparations of whole zoea I and decapodid III, and in juvenile and adult river shrimp gills. Modulation of (Na+, K+)-ATPase activity is ontogenetic stage-specific, and particularly distinct between juveniles and adults. Although both gill enzymes exhibit two different sites for K+ and NH4 + binding, in the juvenile enzyme, these two sites are equivalent: binding by both ions results in slightly stimulated activity compared to that of a single ionic species. In the adult enzyme, the sites are not equivalent: when one ion occupies its specific binding site, (Na+, K+)-ATPase activity is stimulated synergistically by ≈50% on binding of the complementary ion. Immunolocalization reveals the enzyme to be distributed predominantly throughout the intralamellar septum in the gill lamellae of juveniles and adults. Western blot analyses demonstrate a single immunoreactive band, suggesting a single (Na+, K+)-ATPase α-subunit isoform that is distributed into different density membrane fractions, independently of ontogenetic stage. We propose a model for the modulation by K+ and NH4 + of gill (Na+, K+)-ATPase activity. These findings suggest that the gill enzyme may be regulated by NH4 + during ontogenetic development in M. amazonicum. PMID:24586919

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

Phytoremediation of Ionic and Methylmercury Pollution

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

Richard Meagher

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species.

Ionic liquid-assisted multiwalled carbon nanotube-dispersive micro-solid phase extraction for sensitive determination of inorganic As species in garlic samples by electrothermal atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Grijalba, Alexander Castro; Escudero, Leticia B.; Wuilloud, Rodolfo G.

2015-08-01

A highly sensitive dispersive micro-solid phase extraction (D-μ-SPE) method combining an ionic liquid (IL) and multi-walled carbon nanotubes (MWCNTs) for inorganic As species (As(III) and As(V)) species separation and determination in garlic samples by electrothermal atomic absorption spectrometry (ETAAS) was developed. Trihexyl(tetradecil)phosphonium chloride IL was used to form an ion pair with the arsenomolybdate complex obtained by reaction of As(V) with molybdate ion. Afterwards, 1.0 mg of MWCNTs was dispersed for As(V) extraction and the supernatant was separated by centrifugation. MWCNTs were re-dispersed with tetradecyltrimethylammonium bromide surfactant and ultrasound followed by direct injection into the graphite furnace of ETAAS for As determination. Pyrolysis and atomization conditions were carefully studied for complete decomposition of MWCNTs and IL matrices. Under optimum conditions, an extraction efficiency of 100% and a preconcentration factor of 70 were obtained with 5 mL of garlic extract. The detection limit was 7.1 ng L- 1 and the relative standard deviations (RSDs) for six replicate measurements at 5 μg L- 1 of As were 5.4% and 4.8% for As(III) and As(V), respectively. The proposed D-μ-SPE method allowed the efficient separation and determination of inorganic As species in a complex matrix such as garlic extract.

Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

NASA Astrophysics Data System (ADS)

Kausteklis, Jonas; Aleksa, Valdemaras; Iramain, Maximiliano A.; Brandán, Silvia Antonia

2018-07-01

The cation-anion interactions present in the 1-butyl-3-methylimidazolium nitrate ionic liquid [BMIm][NO3] were studied by using density functional theory (DFT) calculations and the experimental FT-Raman spectrum in liquid phase and its available FT-IR spectrum. For the three most stable conformers found in the potential energy surface and their 1-butyl-3-methylimidazolium [BMIm] cation, the atomic charges, molecular electrostatic potentials, stabilization energies, bond orders and topological properties were computed by using NBO and AIM calculations and the hybrid B3LYP level of theory with the 6-31G* and 6-311++G** basis sets. The force fields, force constants and complete vibrational assignments were also reported for those species by using their internal coordinates and the scaled quantum mechanical force field (SQMFF) approach. The dimeric species of [BMIm][NO3] were also considered because their presence could probably explain the most intense bands observed at 1344 and 1042 cm-1 in both experimental FT-IR and FT-Raman spectra, respectively. The geometrical parameters suggest monodentate cation-anion coordination while the studies by charges, NBO and AIM calculations support bidentate coordinations between those two species. Additionally several quantum chemical descriptors were also calculated in order to interpret various molecular properties such as electronic structure, reactivity of those species and predict their gas phase behaviours.

Theoretical Studies of Group IVA and Group IVB Chemistry

DTIC Science & Technology

2012-01-13

novel ionic liquids . We have performed very high level CCSD(T) calculations on one such species, Al13- to predict its ionization potential in nearly...Precursors. Polyhedral oligomeric silsesquioxanes (POSS) are three- dimensional Si-O cage compounds that have many uses, because of their resistance

THE ROLE OF INORGANIC ION IMBALANCE IN AQUATIC TOXICITY TESTING

EPA Science Inventory

Effluent toxicity testing methods have been well defined, but to a large part have not attempted to segregate the effects of active ionic concentrations and ion imbalances upon test and species performances. The role that various total dissolved solids in effluents have on regula...

Sunlight-Driven Reduction of Silver Ions by Natural Organic Matter: Formation and Transformation of Silver Nanoparticles

EPA Science Inventory

Photobiogeochemical reactions involving metal species can be a source of naturally occurring nanoscale materials in the aquatic environment. This study demonstrates that, under simulated sunlight exposure, ionic Ag is photoreduced in river water or synthetic natural water samples...

Magnetomotive room temperature dicationic ionic liquid: a new concept toward centrifuge-less dispersive liquid-liquid microextraction.

PubMed

Beiraghi, Asadollah; Shokri, Masood; Seidi, Shahram; Godajdar, Bijan Mombani

2015-01-09

A new centrifuge-less dispersive liquid-liquid microextraction technique based on application of magnetomotive room temperature dicationic ionic liquid followed by electrothermal atomic absorption spectrometry (ETAAS) was developed for preconcentration and determination of trace amount of gold and silver in water and ore samples, for the first time. Magnetic ionic liquids not only have the excellent properties of ionic liquids but also exhibit strong response to an external magnetic field. These properties provide more advantages and potential application prospects for magnetic ionic liquids than conventional ones in the fields of extraction processes. In this work, thio-Michler's ketone (TMK) was used as chelating agent to form Ag/Au-TMK complexes. Several important factors affecting extraction efficiency including extraction time, rate of vortex agitator, pH of sample solution, concentration of the chelating agent, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) were 3.2 and 7.3ngL(-1) with the preconcentration factors of 245 and 240 for Au and Ag, respectively. The precision values (RSD%, n=7) were 5.3% and 5.8% at the concentration level of 0.05μgL(-1) for Au and Ag, respectively. The relative recoveries for the spiked samples were in the acceptable range of 96-104.5%. The results demonstrated that except Hg(2+), no remarkable interferences are created by other various ions in the determination of Au and Ag, so that the tolerance limits (WIon/WAu or Ag) of major cations and anions were in the range of 250-1000. The validated method was successfully applied for the analysis of Au and Ag in some water and ore samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species.

PubMed

Brites, Vincent; Cimas, Alvaro; Spezia, Riccardo; Sieffert, Nicolas; Lisy, James M; Gaigeot, Marie-Pierre

2015-03-10

Combined theoretical DFT-MD and RRKM methodologies and experimental spectroscopic infrared predissociation (IRPD) strategies to map potential energy surfaces (PES) of complex ionic clusters are presented, providing lowest and high energy conformers, thresholds to isomerization, and cluster formation pathways. We believe this association not only represents a significant advance in the field of mapping minima and transition states on the PES but also directly measures dynamical pathways for the formation of structural conformers and isomers. Pathways are unraveled over picosecond (DFT-MD) and microsecond (RRKM) time scales while changing the amount of internal energy is experimentally achieved by changing the loss channel for the IRPD measurements, thus directly probing different kinetic and isomerization pathways. Demonstration is provided for Li(+)(H2O)3,4 ionic clusters. Nonstatistical formation of these ionic clusters by both direct and cascade processes, involving isomerization processes that can lead to trapping of high energy conformers along the paths due to evaporative cooling, has been unraveled.

Combinatorial ligand libraries as a two-dimensional method for proteome analysis.

PubMed

Santucci, Laura; Candiano, Giovanni; Petretto, Andrea; Lavarello, Chiara; Bruschi, Maurizio; Ghiggeri, Gian Marco; Citterio, Attilio; Righetti, Pier Giorgio

2013-07-05

The present report tries to assess the possibility of performing capture of proteomes via combinatorial peptide ligand libraries (CPLL) in a two-dimensional (2D) mode, i.e. via orthogonal complementarity in the capture phase. To that aim, serum proteins are captured at physiological pH either at low ionic strength (25mM NaCl) or at high concentrations of lyotropic salts of the Hofmeister series (1M ammonium sulphate) favouring hydrophobic interaction. Indeed such 2D mechanisms seems to be operative, since 52% of the captured proteins are common to the two capture modes, 20% are specific only of the "ionic" interaction mode and 28% are found only in the "hydrophobically" driven interaction. As an additional bonus, losses of protein species from the initial sample, one of the major drawbacks of CPLLs, are diminished to about 5% and are found only in the ionic capture, whereas the hydrophobically engendered capture is loss-free. Copyright © 2013 Elsevier B.V. All rights reserved.

Aqueous ionic liquids and their effects on protein structures: an overview on recent theoretical and experimental results

NASA Astrophysics Data System (ADS)

Smiatek, Jens

2017-06-01

Ionic liquids (ILs) are used in a variety of technological and biological applications. Recent experimental and simulation results reveal the influence of aqueous ionic liquids on the stability of protein and enzyme structures. Depending on different parameters like the concentration and the ion composition, one can observe distinct stabilization or denaturation mechanisms for various ILs. In this review, we summarize the main findings and discuss the implications with regard to molecular theories of solutions and specific ion effects. A preferential binding model is introduced in order to discuss protein-IL effects from a statistical mechanics perspective. The value of the preferential binding coefficient determines the strength of the ion influence and indicates a shift of the chemical equilibrium either to the native or the denatured state of the protein. We highlight the role of water in order to explain the self-association behavior of the IL species and discuss recent experimental and simulation results in the light of the observed binding effects.

Semiconductor of spinons: from Ising band insulator to orthogonal band insulator.

PubMed

Farajollahpour, T; Jafari, S A

2018-01-10

We use the ionic Hubbard model to study the effects of strong correlations on a two-dimensional semiconductor. The spectral gap in the limit where on-site interactions are zero is set by the staggered ionic potential, while in the strong interaction limit it is set by the Hubbard U. Combining mean field solutions of the slave spin and slave rotor methods, we propose two interesting gapped phases in between: (i) the insulating phase before the Mott phase can be viewed as gapping a non-Fermi liquid state of spinons by the staggered ionic potential. The quasi-particles of underlying spinons are orthogonal to physical electrons, giving rise to the 'ARPES-dark' state where the ARPES gap will be larger than the optical and thermal gap. (ii) The Ising insulator corresponding to ordered phase of the Ising variable is characterized by single-particle excitations whose dispersion is controlled by Ising-like temperature and field dependences. The temperature can be conveniently employed to drive a phase transition between these two insulating phases where Ising exponents become measurable by ARPES and cyclotron resonance. The rare earth monochalcogenide semiconductors where the magneto-resistance is anomalously large can be a candidate system for the Ising band insulator. We argue that the Ising and orthogonal insulating phases require strong enough ionic potential to survive the downward renormalization of the ionic potential caused by Hubbard U.

Replica-exchange molecular dynamics simulations of cellulose solvated in water and in the ionic liquid 1-butyl-3-methylimidazolium chloride

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

Mostofian, Barmak; Cheng, Xiaolin; Smith, Jeremy C.

2014-09-02

Ionic liquids have become a popular solvent for cellulose pretreatment in biorefineries due to their efficiency in dissolution and their reusability. Understanding the interactions between cations, anions, and cellulose is key to the development of better solvents and the improvement of pretreatment conditions. While previous studies described the interactions between ionic liquids and cellulose fibers, shedding light on the initial stages of the cellulose dissolution process, we study the end state of that process by exploring the structure and dynamics of a single cellulose decamer solvated in 1-butyl-3-methyl-imidazolium chloride (BmimCl) and in water using replica-exchange molecular dynamics. In both solvents,more » global structural features of the cellulose chain are similar. However, analyses of local structural properties show that cellulose explores greater conformational variability in the ionic liquid than in water. For instance, in BmimCl the cellulose intramolecular hydrogen bond O3H'••• O5 is disrupted more often resulting in greater flexibility of the solute. Our results indicate that the cellulose chain is more dynamic in BmimCl than in water, which may play a role in the favorable dissolution of cellulose in the ionic liquid. Here, the calculation of the configurational entropy of the cellulose decamer confirms its higher conformational flexibility in BmimCl than in water at elevated temperatures.« less

Semiconductor of spinons: from Ising band insulator to orthogonal band insulator

NASA Astrophysics Data System (ADS)

Farajollahpour, T.; Jafari, S. A.

2018-01-01

We use the ionic Hubbard model to study the effects of strong correlations on a two-dimensional semiconductor. The spectral gap in the limit where on-site interactions are zero is set by the staggered ionic potential, while in the strong interaction limit it is set by the Hubbard U. Combining mean field solutions of the slave spin and slave rotor methods, we propose two interesting gapped phases in between: (i) the insulating phase before the Mott phase can be viewed as gapping a non-Fermi liquid state of spinons by the staggered ionic potential. The quasi-particles of underlying spinons are orthogonal to physical electrons, giving rise to the ‘ARPES-dark’ state where the ARPES gap will be larger than the optical and thermal gap. (ii) The Ising insulator corresponding to ordered phase of the Ising variable is characterized by single-particle excitations whose dispersion is controlled by Ising-like temperature and field dependences. The temperature can be conveniently employed to drive a phase transition between these two insulating phases where Ising exponents become measurable by ARPES and cyclotron resonance. The rare earth monochalcogenide semiconductors where the magneto-resistance is anomalously large can be a candidate system for the Ising band insulator. We argue that the Ising and orthogonal insulating phases require strong enough ionic potential to survive the downward renormalization of the ionic potential caused by Hubbard U.

Microfludic Device for Creating Ionic Strength Gradients over DNA Microarrays for Efficient DNA Melting Studies and Assay Development

PubMed Central

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients. PMID:19277213

Microfludic device for creating ionic strength gradients over DNA microarrays for efficient DNA melting studies and assay development.

PubMed

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients.

Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

PubMed

Faria, Luiz F O; Ribeiro, Mauro C C

2015-11-05

Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

Two-site ionic labeling with pyranine: implications for structural dynamics studies of polymers and polypeptides by time-resolved fluorescence anisotropy.

PubMed

Sharma, Jai; Tleugabulova, Dina; Czardybon, Wojciech; Brennan, John D

2006-04-26

Time-resolved fluorescence anisotropy (TRFA) is widely used to study dynamic motions of biomolecules in a variety of environments. However, depolarization due to rapid side chain motions often complicates the interpretation of anisotropy decay data and interferes with the accurate observation of segmental motions. Here, we demonstrate a new method for two-point ionic labeling of polymers and biomolecules that have appropriately spaced amino groups using the fluorescent probe 8-hydroxyl-1,3,6-trisulfonated pyrene (pyranine). TRFA analysis shows that such labeling provides a more rigid attachment of the fluorophore to the macromolecule than the covalent or single-point ionic labeling of amino groups, leading to time-resolved anisotropy decays that better reflect the backbone motion of the labeled polymer segment. Optimal coupling of pyranine to biomolecule dynamics is shown to be obtained for appropriately spaced Arg groups, and in such cases the ionic binding is stable up to 150 mM ionic strength. TRFA was used to monitor the behavior of pyranine-labeled poly(allylamine) (PAM) and poly-d-lysine (PL) in sodium silicate derived sol-gel materials and revealed significant restriction of backbone motion upon entrapment for both polymers, an observation that was not readily apparent in a previous study with entrapped fluorescein-labeled PAM and PL. The implications of these findings for fluorescence studies of polymer and biomolecule dynamics are discussed.

Amphiphilic interactions of ionic liquids with lipid biomembranes: a molecular simulation study.

PubMed

Yoo, Brian; Shah, Jindal K; Zhu, Yingxi; Maginn, Edward J

2014-11-21

Current bottlenecks in the large-scale commercial use of many ionic liquids (ILs) include their high costs, low biodegradability, and often unknown toxicities. As a proactive effort to better understand the molecular mechanisms of ionic liquid toxicities, the work herein presents a comprehensive molecular simulation study on the interactions of 1-n-alkyl-3-methylimidazolium-based ILs with a phosphatidylcholine (PC) lipid bilayer. We explore the effects of increasing alkyl chain length (n = 4, 8, and 12) in the cation and anion hydrophobicity on the interactions with the lipid bilayer. Bulk atomistic molecular dynamics (MD) simulations performed at millimolar (mM) IL concentrations show spontaneous insertion of cations into the lipid bilayer regardless of the alkyl chain length and a favorable orientational preference once a cation is inserted. Cations also exhibit the ability to "flip" inside the lipid bilayer (as is common for amphiphiles) if partially inserted with an unfavorable orientation. Moreover, structural analysis of the lipid bilayer show that cationic insertion induces roughening of the bilayer surface, which may be a precursor to bilayer disruption. To overcome the limitation in the timescale of our simulations, free energies for a single IL cation and anion insertion have been determined based on potential of mean force calculations. These results show a decrease in free energy in response to both short and long alkyl chain IL cation insertion, and likewise for a single hydrophobic anion insertion, but an increase in free energy for the insertion of a hydrophilic chloride anion. Both bulk MD simulations and free energy calculations suggest that toxicity mechanisms toward biological systems are likely caused by ILs behaving as ionic surfactants. [Yoo et al., Soft Matter, 2014].

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

Effect of Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilis AX101.

PubMed

Gyamerah, M; Ampaw-Asiedu, M; Mackey, J; Menezes, B; Woldesenbet, S

2018-06-01

The potential of large-scale lignocellulosic biomass hydrolysis to fermentable sugars using ionic liquids has increased interest in this green chemistry route to fermentation for fuel-ethanol production. The ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride compared to other reported ionic liquids has the advantage of hydrolysing lignocellulosic biomass to reducing sugars at catalytic concentrations (≤0·032 mol l -1 ) in a single step. However, effects of this ionic liquid on co-fermentation of glucose, xylose and arabinose to ethanol by recombinant Zymomonas mobilisAX101 has not been studied. Authentic glucose, xylose and arabinose were used to formulate fermentation media at varying catalytic 1-(1-propylsulfonic)-3-methylimidazolium chloride concentrations for batch co-fermentation of the sugars using Z. mobilisAX101. The results showed that at 0·008, 0·016 and 0·032 mol l -1 ionic liquid in the culture medium, cell growth decreased by 10, 27 and 67% respectively compared to the control. Ethanol yields were 62·6, 61·8, 50·5 and 23·1% for the control, 0·008, 0·016 and 0·032 mol l -1 ionic liquid respectively. The results indicate that lignocellulosic biomass hydrolysed using 0·008 mol l -1 of 1-(1-propylsulfonic)-3-methylimidazolium chloride would eliminate an additional separation step and provide a ready to use fermentation substrate. This is the first reported study of the effect of the Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilisAX101 in batch culture. Growth on and co-fermentation of the sugars by Z. mobilisAX 101 with no significant inhibition by the ionic liquid at the same catalytic amounts of 0·008 mol l -1 used to hydrolyse lignocellulosic biomass to reducing sugars overcome two major hurdles that adversely affect the process economics of large-scale industrial cellulosic fuel ethanol production; the energy-intensive hydrolysis and ionic liquid separation steps. © 2018 The Society for Applied Microbiology.

Simultaneous separation and determination of six arsenic species in rice by anion-exchange chromatography with inductively coupled plasma mass spectrometry.

PubMed

Ma, Li; Yang, Zhaoguang; Tang, Jie; Wang, Lin

2016-06-01

The simultaneous separation and determination of arsenite As(III), arsenate As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC) in rice samples have been carried out in one single anion-exchange column run by high-performance liquid chromatography with inductively coupled plasma mass spectrometry. To estimate the effect of variables on arsenic (As) speciation, the chromatographic conditions including type of competing anion, ionic strength, pH of elution buffer, and flow rate of mobile phase have been investigated by a univariate approach. Under the optimum chromatographic conditions, baseline separation of six As species has been achieved within 10 min by gradient elution program using 4 mM NH4 HCO3 at pH 8.6 as mobile phase A and 4 mM NH4 HCO3 , 40 mM NH4 NO3 at pH 8.6 as mobile phase B. The method detection limits for As(III), As(V), MMA, DMA, AsB, and AsC were 0.4, 0.9, 0.2, 0.4, 0.5, and 0.3 μg/kg, respectively. The proposed method has been applied to separation and quantification of As species in real rice samples collected from Hunan Province, China. The main As species detected in all samples were As(III), As(V) and DMA, with inorganic As accounting for over 80% of total As in these samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolutionary adaptation of muscle power output to environmental temperature: force-velocity characteristics of skinned fibres isolated from antarctic, temperate and tropical marine fish.

PubMed

Johnston, I A; Altringham, J D

1985-09-01

Single fast fibres were isolated from the myotomal muscles of icefish (Chaenocephalus aceratus Lönnberg, Antarctica), North Sea Cod (Gadus morhua L.) and Pacific Blue Marlin (Makaira nigricans Wakiya, Hawaii). Fibres were chemically skinned with the non-ionic detergent Brij-58. Maximum tensions (Po, kN m-2) developed at the characteristic body temperature of each species are 231 for icefish (-1 degree C), 187 for cod (8 degrees C) and 156 for marlin (20 degrees C). At 0 degree C Po is 7 times higher for fibres from the icefish than from the marlin. Fibres from icefish and cod failed to relax completely following activations at temperatures above approximately 12 degrees C. The resultant post-contraction force is associated with a proportional increase in stiffness, suggesting the formation of a population of Ca-insensitive cross bridges. At 10 degrees C there is little interspecific variation in unloaded contraction velocity (Vmax) among the three species. Vmax (muscle lengths s-1) at normal body temperatures are 0.9 for icefish (-1 degree C), 1.0 for cod (8 degrees C) and 3.4 for marlin (20 degrees C). The force-velocity (P-V) relationship becomes progressively more curved with increasing temperature for all three species. Maximum power output for the fast muscle fibres from the Antarctic species at -1 degree C is around 60% of that of the tropical fish at 20 degrees C. Evolutionary temperature compensation of muscle power output appears largely to involve differences in the ability of cross bridges to generate force.

Flame and solution syntheses of high-dimensional homo- and hetero-structured nanomaterials

NASA Astrophysics Data System (ADS)

Dong, Zhizhong

Tungsten-oxide and molybdenum-oxide nanostructures are fabricated directly from the surfaces of metal substrates using counter-flow diffusion-flame synthesis method, which allows for correlation of morphologies with local conditions. Computational simulations aid in tailoring the flame structure with respect to chemical species and temperature. Furthermore, methane flames are compared with hydrogen flames, which only have H2O (and no CO2) as product species. The temperature profiles of the methane and hydrogen flames are strategically matched in order to compare the effect of chemical species produced by the flame which serve as reactants for nanostructure growth. Single-crystalline, well-vertically-aligned, and dense WO2.9 nanowires (diameters of 20-50 nm, lengths of >10 microm) are obtained at a gas-phase temperature of 1720 K, where the CO2 route is presumed to seed the growth of nanowires at the nucleation stage, with subsequent vapor-solid growth. Similarly, single-crystalline, vertically-aligned, and dense MoO 2 nanoplates (thicknesses of 60-80 nm, widths of 200-450 nm, lengths of 1-2 microm) are obtained at 1720 K. Nanoheterostructures are fabricated by decorating/coating the above flame-synthesized tungsten-oxide nanowires with other materials using an aqueous solution synthesis method. With WO 2.9 nanowires serving as the scaffold, sequential growth of hexagonal ZnO nanoplates, Zn2SnO4 nanocubes, and SnO2 nanoparticles are attained for different Zn2+:Sn2+ concentration ratios. High-resolution transmission electron microscopy (HRTEM) of the interfaces at the nanoheterojunctions show atomically abrupt interfaces for ZnO/WO2.9 and Zn2SnO4/WO2.9, despite lattice mismatches. Separately, co-axial nanoheterostructures are fabricated using ionic-liquid solutions, where single-crystal nanoscale Al layer are electrodeposited on the surfaces of the above flame-synthesized WO2.9 nanowires. These tungsten-oxide/aluminum coaxial nanowire arrays constitute thermite nanocomposites with high reactivity. These geometries not only present an avenue to tailor heat-release characteristics due to anisotropic arrangement of fuel and oxidizer, but also possibly eliminate or at least minimize the presence of Al2O3 passivation films between the aluminum and metal oxide.

Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

NASA Astrophysics Data System (ADS)

Ams, D.; Swanson, J. S.; Reed, D. T.

2010-12-01

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic strength effects as the electronic double layer is compressed with increasing ionic strength. These results further highlight the importance of electrostatic interactions in the adsorption process between dissolved metals and bacterial surfaces. This work expands the understanding of actinide-bacteria adsorption phenomena to high ionic strength environmental conditions that are relevant as an aid to predicting Np(V) fate and transport behavior in areas such as the vicinity of salt-based nuclear waste repositories and high ionic-strength groundwaters at DOE sites.

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

Using field data to assess the tolerance of freshwater fish to elevated ionic concentrations

EPA Science Inventory

We used field data of fish occurrences and specific conductivity to assess the tolerance of freshwater fish to elevated ions. The concentration at which a species was expected to no longer be observed [the extirpation concentration (XC95)] was identified from the 95th percentile ...

The role of the anion in the toxicity of imidazolium ionic liquids.

PubMed

Biczak, Robert; Pawłowska, Barbara; Bałczewski, Piotr; Rychter, Piotr

2014-06-15

From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish. Copyright © 2014 Elsevier B.V. All rights reserved.

Electroosmotic flow and ionic conductance in a pH-regulated rectangular nanochannel

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Sadeghi, Arman

2017-06-01

Infinite series solutions are obtained for electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties of long pH-regulated rectangular nanochannels of low surface potential utilizing the double finite Fourier transform method. Closed form expressions are also obtained for channels of large height to width ratio for which the depthwise variations vanish. Neglecting the Stern layer impact, the effects of EDL (Electric Double Layer) overlap, multiple ionic species, and association/dissociation reactions on the surface are all taken into account. Moreover, finite-element-based numerical simulations are conducted to account for the end effects as well as to validate the analytical solutions. We show that, with the exception of the migratory ionic conductivity, all the physicochemical parameters are strong functions of the channel aspect ratio. Accordingly, a slit geometry is not a good representative of a rectangular channel when the width is comparable to the height. It is also observed that the distribution of the electrical potential is not uniform over the surface of a charge-regulated channel. In addition, unlike ordinary channels for which an increase in the background salt concentration is always accompanied by higher flow rates, quite the opposite may be true for a pH-regulated duct at higher salt concentrations.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Proceedings of the NATO Advances Research Workshop on Diamond Based Composites, Saint Petersburg, Russia, June 21-22, 1997, Volume 38

DTIC Science & Technology

1997-06-01

composites. The topics ranged from molecular clusters, nanophase materials, growth, processing, and synthesis. Commercial composite materials have been on...example, an analysis of the emission from a GaAs target shows mainly (99.4%) neutral Ga and As atoms. [63] However, the fraction of molecular species...sputtered from ionic crystals can be considerably higher. [64] There is evidence that a large fraction of the molecular species originate from

Capillary ion chromatography with on-column focusing for ultra-trace analysis of methanesulfonate and inorganic anions in limited volume Antarctic ice core samples.

PubMed

Rodriguez, Estrella Sanz; Poynter, Sam; Curran, Mark; Haddad, Paul R; Shellie, Robert A; Nesterenko, Pavel N; Paull, Brett

2015-08-28

Preservation of ionic species within Antarctic ice yields a unique proxy record of the Earth's climate history. Studies have been focused until now on two proxies: the ionic components of sea salt aerosol and methanesulfonic acid. Measurement of the all of the major ionic species in ice core samples is typically carried out by ion chromatography. Former methods, whilst providing suitable detection limits, have been based upon off-column preconcentration techniques, requiring larger sample volumes, with potential for sample contamination and/or carryover. Here, a new capillary ion chromatography based analytical method has been developed for quantitative analysis of limited volume Antarctic ice core samples. The developed analytical protocol applies capillary ion chromatography (with suppressed conductivity detection) and direct on-column sample injection and focusing, thus eliminating the requirement for off-column sample preconcentration. This limits the total sample volume needed to 300μL per analysis, allowing for triplicate sample analysis with <1mL of sample. This new approach provides a reliable and robust analytical method for the simultaneous determination of organic and inorganic anions, including fluoride, methanesulfonate, chloride, sulfate and nitrate anions. Application to composite ice-core samples is demonstrated, with coupling of the capillary ion chromatograph to high resolution mass spectrometry used to confirm the presence and purity of the observed methanesulfonate peak. Copyright © 2015 Elsevier B.V. All rights reserved.

Physiological and biochemical responses of wheat (Triticum aestivum L.) seedlings to three imidazolium-based ionic liquids in soil.

PubMed

Xu, Yaqi; Wang, Jun; Zhu, Lusheng; Du, Zhongkun; Wang, Jinhua; Wei, Kai

2018-01-01

Ionic liquids (ILs) are considered environmentally friendly solvents and are widely applied in various fields; however, some researchers have noted the toxicity of ILs to plants cultivated in nutrient solution. To evaluate the toxicities of ILs to wheat seedlings in soil, the natural growth environment of plants, a study was performed using three imidazolium-based ionic liquids with different anions: 1-octyl-3-methylimidazolium chloride ([C 8 mim]Cl), 1-octyl-3-methylimidazolium bromide ([C 8 mim]Br) and 1-octyl-3-methylimidazolium tetrafluoroborate ([C 8 mim]BF 4 ). After 13 d of exposure to these three ILs at 0, 100, 200, 400, 600 and 800 mg kg -1 in brown soil, wheat seedlings were randomly sampled to evaluate growth (shoot length, root length, pigment content and proline content), lipid peroxidation, oxygen species (H 2 O 2 and O 2 - ) and activities of the detoxification enzyme glutathione-s-transferase and other antioxidant enzymes, including superoxide dismutase, catalase and peroxidase. The experimental results showed that all three ILs had inhibitory effects on the growth of wheat seedlings and induced the generation of reactive oxygen species, which indicated that the wheat seedlings suffered oxidative stress. Moreover, antioxidant enzyme activity was enhanced after exposure to [C 8 mim]Cl, [C 8 mim]Br and [C 8 mim]BF 4 , demonstrating that oxidative damage may be the primary underlying mechanism of IL toxicity in wheat. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dielectric constant of ionic solutions: a field-theory approach.

PubMed

Levy, Amir; Andelman, David; Orland, Henri

2012-06-01

We study the variation of the dielectric response of a dielectric liquid (e.g. water) when a salt is added to the solution. Employing field-theoretical methods, we expand the Gibbs free energy to first order in a loop expansion and calculate self-consistently the dielectric constant. We predict analytically the dielectric decrement which depends on the ionic strength in a complex way. Furthermore, a qualitative description of the hydration shell is found and is characterized by a single length scale. Our prediction fits rather well a large range of concentrations for different salts using only one fit parameter related to the size of ions and dipoles.

Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength.

PubMed

Veen, Sandra J; Kegel, Willem K

2009-11-19

We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like assemblies. This instability occurs at significantly lower ionic strength than the colloidal stability limit and only becomes evident after a relatively long time. For the polyoxometalate, abbreviated as {Mo(72)Fe(30)}, it is shown that the structural stability limit of POM-shells lies between a NaCl concentration of 1.00 and 5.00 mM in aqueous solution.

Numerical simulation of proton exchange membrane fuel cells at high operating temperature

NASA Astrophysics Data System (ADS)

Peng, Jie; Lee, Seung Jae

A three-dimensional, single-phase, non-isothermal numerical model for proton exchange membrane (PEM) fuel cell at high operating temperature (T ≥ 393 K) was developed and implemented into a computational fluid dynamic (CFD) code. The model accounts for convective and diffusive transport and allows predicting the concentration of species. The heat generated from electrochemical reactions, entropic heat and ohmic heat arising from the electrolyte ionic resistance were considered. The heat transport model was coupled with the electrochemical and mass transport models. The product water was assumed to be vaporous and treated as ideal gas. Water transportation across the membrane was ignored because of its low water electro-osmosis drag force in the polymer polybenzimidazole (PBI) membrane. The results show that the thermal effects strongly affect the fuel cell performance. The current density increases with the increasing of operating temperature. In addition, numerical prediction reveals that the width and distribution of gas channel and current collector land area are key optimization parameters for the cell performance improvement.

Anomalous optical emission in hot dense oxygen

NASA Astrophysics Data System (ADS)

Santoro, Mario; Gregoryanz, Eugene; Mao, Ho-kwang; Hemley, Russell J.

2007-11-01

We report the observation of unusually strong, broad-band optical emission peaked between 590 and 650 nm when solid and fluid oxygen are heated by a near infrared laser at pressures from 3 to 46 GPa. In situ Raman spectra of oxygen were collected and corresponding temperatures were measured from the Stokes/anti-Stokes intensity ratios of vibrational transitions. The intense optical emission overwhelmed the Raman spectrum at temperatures exceeding 750 K. The spectrum was found to be much narrower than Planck-type thermal emission, and the intensity increase with input power was much steeper than expected for the thermal emission. The result places an important general caveat on calculating temperatures based on optical emission spectra in high-pressure laser-heating experiments. The intense emission in oxygen is photo-induced rather than being purely thermal, through multiphoton or multi-step single photon absorption processes related to the interaction with infrared radiation. The results suggest that short lived ionic species are induced by this laser-matter interaction.

Determination of fluoroquinolone antibiotics via ionic-liquid-based, salt-induced, dual microextraction in swine feed.

PubMed

Wang, Huili; Gao, Ming; Gao, Jiajia; Yu, Nana; Huang, Hong; Yu, Qing; Wang, Xuedong

2016-09-01

In conventional microextraction procedures, the disperser (organic solvent or ionic liquid) is left in the aqueous phase and discarded after finishing the microextraction process. Because the disperser is water-soluble, it results in low extraction recovery for polar compounds. In this investigation, an ionic-liquid-based microextraction (ILBME) was integrated with salting-out assisted liquid-liquid microextraction (SALLME) to build an ionic-liquid-based, salt-induced, dual microextraction (ILSDME) for isolation of five fluoroquinolone antibiotics (FQs) with high polarity (log P, -1.0 to 1.0). The proposed ILSDME method incorporates a dual microextraction by converting the disperser in the ILBME to the extractor in the SALLME. Optimization of key factors was conducted by integrating single-factor experiments and central composite design. The optimized experimental parameters were 80 μL [C8MIM][PF6] as extractor, 505 μL acetone as disperser, pH = 2.0, 4.1 min extraction time, and 4.2 g of Na2SO4. Under optimized conditions, high ERs (90.6-103.2 %) and low LODs (0.07-0.61 μg kg(-1)) were determined for five FQs in swine feed. Experimental precision based on RSDs was 1.4-5.2 % for intra-day and 2.4-6.9 % for inter-day analyses. The combination of ILBME with SALLME increased FQ recoveries by 15-20 % as compared with SALLME, demonstrating that the ILSDME method can enhance extraction efficiency for polar compounds compared to single-step microextraction. Therefore, the ILSDME method developed in this study has wide application for pretreatment of moderately to highly polar pollutants in complex matrices. Graphical Abstract A dual microextraction was developed by integrating ionic-liquid-based microextraction with salting-out assisted liquid-liquid microextraction for isolation of five fluoroquinolone antibiotics (FQs) with high polarity (log P = -1.0 to 1.0). The principle of dual microextraction is based on converting the remaining disperser from the first microextraction into an extractor in the second microextraction. Single-factor experiment and central composite design were applied for optimizing operational parameters using 3D response surfaces and contour lines. Under optimized conditions, the method provided high extraction recoveries and low LODs for five FQs in swine feed. The prominent advantage of the dual microextraction is rapid and highly efficient extraction of moderately to highly polar fluoroquinolones from complex matrices.

Effect of Aperture Field Variability, Flow Rate, and Ionic Strength on Colloid Transport in Single Fractures: Laboratory-Scale Experiments and Numerical Simulation

NASA Astrophysics Data System (ADS)

Zheng, Q.; Dickson, S.; Guo, Y.

2007-12-01

A good understanding of the physico-chemical processes (i.e., advection, dispersion, attachment/detachment, straining, sedimentation etc.) governing colloid transport in fractured media is imperative in order to develop appropriate bioremediation and/or bioaugmentation strategies for contaminated fractured aquifers, form management plans for groundwater resources to prevent pathogen contamination, and identify suitable radioactive waste disposal sites. However, research in this field is still in its infancy due to the complex heterogeneous nature of fractured media and the resulting difficulty in characterizing this media. The goal of this research is to investigate the effects of aperture field variability, flow rate and ionic strength on colloid transport processes in well characterized single fractures. A combination of laboratory-scale experiments, numerical simulations, and imaging techniques were employed to achieve this goal. Transparent replicas were cast from natural rock fractures, and a light transmission technique was employed to measure their aperture fields directly. The surface properties of the synthetic fractures were characterized by measuring the zeta-potential under different ionic strengths. A 33 (3 increased to the power of 3) factorial experiment was implemented to investigate the influence of aperture field variability, flow rate, and ionic strength on different colloid transport processes in the laboratory-scale fractures, specifically dispersion and attachment/detachment. A fluorescent stain technique was employed to photograph the colloid transport processes, and an analytical solution to the one-dimensional transport equation was fit to the colloid breakthrough curves to calculate the average transport velocity, dispersion coefficient, and attachment/detachment coefficient. The Reynolds equation was solved to obtain the flow field in the measured aperture fields, and the random walk particle tracking technique was employed to model the colloid transport experiments. The images clearly show the development of preferential pathways for colloid transport in the different aperture fields and under different flow conditions. Additionally, a correlation between colloid deposition and fracture wall topography was identified. This presentation will demonstrate (1) differential transport between colloid and solute in single fractures, and the relationship between differential transport and aperture field statistics; (2) the relationship between the colloid dispersion coefficient and aperture field statistics; and (3) the relationship between attachment/detachment, aperture field statistics, fracture wall topography, flow rate, and ionic strength. In addition, this presentation will provide insight into the application of the random walk particle tracking technique for modeling colloid transport in variable-aperture fractures.

Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca

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

He, Yang; Gu, Meng; Xiao, Haiyan

2016-04-13

Reversible insertion and extraction of ionic species into a host lattice governs the basic operating principle for both rechargeable battery (such as lithium batteries) and electrochromic devices (such as ANA Boeing 787-8 Dreamliner electrochromic window). Intercalation and/or conversion are two fundamental chemical processes for some materials in response to the ion insertion. The interplay between these two chemical processes has never been established. It is speculated that the conversion reaction is initiated by ion intercalation. However, experimental evidence of intercalation and subsequent conversion remains unexplored. Here, using in situ HRTEM and spectroscopy, we captured the atomistic conversion reaction processes duringmore » lithium, sodium and calcium ion insertion into tungsten trioxide (WO3) single crystal model electrodes. An intercalation step right prior to conversion is explicitly revealed at atomic scale for the first time for these three ion species. Combining nanoscale diffraction and ab initio molecular dynamics simulations, it is found that, beyond intercalation, the inserted ion-oxygen bonding formation destabilized the transition-metal framework which gradually shrunk, distorted and finally collapsed to a pseudo-amorphous structure. This study provides a full atomistic picture on the transition from intercalation to conversion, which is of essential for material applications in both secondary ion batteries and electrochromic devices.« less

Evolution of niche preference in Sphagnum peat mosses.

PubMed

Johnson, Matthew G; Granath, Gustaf; Tahvanainen, Teemu; Pouliot, Remy; Stenøien, Hans K; Rochefort, Line; Rydin, Håkan; Shaw, A Jonathan

2015-01-01

Peat mosses (Sphagnum) are ecosystem engineers-species in boreal peatlands simultaneously create and inhabit narrow habitat preferences along two microhabitat gradients: an ionic gradient and a hydrological hummock-hollow gradient. In this article, we demonstrate the connections between microhabitat preference and phylogeny in Sphagnum. Using a dataset of 39 species of Sphagnum, with an 18-locus DNA alignment and an ecological dataset encompassing three large published studies, we tested for phylogenetic signal and within-genus changes in evolutionary rate of eight niche descriptors and two multivariate niche gradients. We find little to no evidence for phylogenetic signal in most component descriptors of the ionic gradient, but interspecific variation along the hummock-hollow gradient shows considerable phylogenetic signal. We find support for a change in the rate of niche evolution within the genus-the hummock-forming subgenus Acutifolia has evolved along the multivariate hummock-hollow gradient faster than the hollow-inhabiting subgenus Cuspidata. Because peat mosses themselves create some of the ecological gradients constituting their own habitats, the classic microtopography of Sphagnum-dominated peatlands is maintained by evolutionary constraints and the biological properties of related Sphagnum species. The patterns of phylogenetic signal observed here will instruct future study on the role of functional traits in peatland growth and reconstruction. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Precipitation chemistry over urban, rural and high altitude Himalayan stations in eastern India

NASA Astrophysics Data System (ADS)

Roy, Arindam; Chatterjee, Abhijit; Tiwari, Suresh; Sarkar, Chirantan; Das, Sanat Kumar; Ghosh, Sanjay Kumar; Raha, Sibaji

2016-11-01

A study of precipitation (rainwater) chemistry during the two consecutive summer monsoon seasons of 2013 and 2014 at a high altitude station (2200 m asl) at eastern Himalaya region (Darjeeling); a typical metropolitan urban location (Kolkata), and a rural environment near the Bay of Bengal (Falta) was conducted. The volume-weighted mean (VWM) concentration shows that total ionic composition was maximum over Kolkata (391 μeq l- 1) followed by Falta (204 μeq l- 1) and Darjeeling (64 μeq l- 1). 85% rain samples were alkaline over Kolkata, whereas, 55 and 65% samples were acidic over Falta and Darjeeling respectively. Ca2 + was the most potential species to completely neutralize the acidity over Kolkata, whereas, NH4+ was the potential species to partially neutralize the acidity over Falta and Darjeeling. The deposition fluxes of anthropogenic and dust species over Kolkata was remarkably higher than Falta and Darjeeling. Anthropogenic and dust chemical species in rainwater were found to be dominant over Kolkata and Falta when the air masses passes from the polluted continental region. Rainwater acidity over Darjeeling was highest when air masses arrived from the Arabian Sea compared to air masses from the Bay of Bengal. Positive matrix factorization model was used for the source apportionment of the ionic species scavenged by rain. Comparable contributions of marine, dust, and anthropogenic sources were identified as major source over Kolkata. The major contributions were identified from marine and fossil fuel burning over Falta, whereas, marine, biomass/coal burning, ammonia from agricultural activities and domestic wastes were identified as the major sources over Darjeeling.

Insight into fast ion migration kinetics of a new hybrid single Li-ion conductor based on aluminate complexes for solid-state Li-ion batteries.

PubMed

Feng, Yancong; Tan, Rui; Zhao, Yan; Gao, Rongtan; Yang, Luyi; Yang, Jinlong; Li, Hao; Zhou, Guofu; Chen, Haibiao; Pan, Feng

2018-03-29

A novel hybrid single Li-ion conductor (SLIC) for a Li-ion solid electrolyte was prepared by mixing aluminate complexes-polyethylene glycol (LiAl-PEG) and polyethylene oxide (PEO) for solid-state Li-ion batteries. The LiAl-PEG/PEO blend possesses high thermal stability and electrochemical stability with an oxidation decomposition voltage up to 4.8 V. Notably, this hybrid SLIC exhibits not only excellent Li-ion migration kinetics, but also good ionic conductivity as high as 4.0 × 10-5 and 2.6 × 10-4 S cm-1 at 30 and 100 °C, respectively, which is much higher than previously reported SLICs. Importantly, by the combination of molecular dynamics simulations and experiment measurements, the mechanisms of Li-ion migration across the SLIC (LiAl-PEG), the salt-in-polymer (LiClO4/PEO) and the optimized SLIC (LiAl-PEG/PEO) were systematically investigated for the first time. The new hopping transport mechanism was verified for the SLIC system at the nanoscale. As for the hybrid SLIC, PEO chains enhance the segmental mobility of the ether-chains bonded with Al atoms, improve the ionicity, and provide extra ionic paths for Li transfer, resulting in the optimized Li-ion migration kinetics of LiAl-PEG/PEO.

Establishing Dual Electrogenerated Chemiluminescence and Multi-Color Electrochromism in Functional Ionic Transition Metal Complexes

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

Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.

A combination of electrochromism and electroluminescence in functional materials could lead to single-layer dual electrochromic/electroluminescent (EC/EL) display devices, capable of simultaneous operation in emissive and reflective modes. Whereas such next generation displays could provide optimal visibility in any ambient lighting situation, materials available that exhibit such characteristics in the active layer are limited due to the required intrinsic multifunctionality (i.e., redox activity, electroluminescence, electrochromism, and ion conductivity) and to date can only be achieved via the rational design of ionic transition-metal complexes. Reported herein is the synthesis and characterization of a new family of acrylate-containing ruthenium (tris)bipyridine-based coordination complexes withmore » multifunctional characteristics. Potential use of the presented compounds in EC/EL devices is established, as they are applied as cross-linked electrochromic films and electrochemiluminescent layers in light-emitting electrochemical cell devices. Electrochromic switching of the polymeric networks between yellow, orange, green, brown and transmissive states is demonstrated, and electrochemiluminescent devices based on the complexes synthesized show red-orange to deep red emission with λ{sub max} ranging from 680 to 722 nm and luminance up to 135 cd/m{sup 2}. Additionally, a dual EC/EL device prototype is presented where light emission and multicolor electrochromism occur from the same pixel comprised of a single active layer, demonstrating a true combination of these properties in ionic transition-metal complexes.« less

Establishing Dual Electrogenerated Chemiluminescence and Multicolor Electrochromism in Functional Ionic Transition-Metal Complexes

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

Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.

A combination of electrochromism and electroluminescence in functional materials could lead to single-layer dual electrochromic/electroluminescent (EC/EL) display devices, capable of simultaneous operation in emissive and reflective modes. Whereas such next generation displays could provide optimal visibility in any ambient lighting situation, materials available that exhibit such characteristics in the active layer are limited due to the required intrinsic multifunctionality (i.e., redox activity, electroluminescence, electrochromism, and ion conductivity) and to date can only be achieved via the rational design of ionic transition-metal complexes. Reported herein is the synthesis and characterization of a new family of acrylate-containing ruthenium (tris)bipyridine-based coordination complexes withmore » multifunctional characteristics. Potential use of the presented compounds in EC/EL devices is established, as they are applied as cross-linked electrochromic films and electrochemiluminescent layers in light-emitting electrochemical cell devices. Electrochromic switching of the polymeric networks between yellow, orange, green, brown and transmissive states is demonstrated, and electrochemiluminescent devices based on the complexes synthesized show red-orange to deep red emission with λmax ranging from 680 to 722 nm and luminance up to 135 cd/m². Additionally, a dual EC/EL device prototype is presented where light emission and multicolor electrochromism occur from the same pixel comprised of a single active layer, demonstrating a true combination of these properties in ionic transition-metal complexes.« less

An improved ionic liquid-based headspace single-drop microextraction-liquid chromatography method for the analysis of camphor and trans-anethole in compound liquorice tablets.

PubMed

He, Xiaowen; Zhang, Fucheng; Jiang, Ye

2012-07-01

A simple, accurate and sensitive ionic liquid-based headspace single-drop microextraction procedure followed by high-performance liquid chromatography was developed and validated for the determination of camphor and trans-anethole in compound liquorice tablets. The volume of the ionic liquid microdrop was increased to 12 µL by modifying the device of the suspended drop. The stability of the microdrop and the sensitivity of the method were improved. Under the optimum experimental conditions, the calculated calibration curves gave acceptable linearity for camphor and trans-anethole with correlation coefficients of 0.9990 and 0.9998, respectively. The repeatability of the proposed method, expressed as relative standard deviation, was below 4.5% (n = 5). The limits of detection for the two target analytes were found to be 9.77 and 1.95 × 10(-2) μg/mL, respectively. In this study, the separation, purification and enrichment were achieved in one step in an airtight system, which reduced the interferences caused by other complicated constituents, increased the signal-to-noise of the method and ensured the accuracy of the results because there was no loss of volatile components. It is expected to be widely applied for sample pretreatment of volatile components with high boiling points in samples with complicated matrices such as the extractions of plants or Chinese traditional drugs.

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

An ionic liquid as a solvent for headspace single drop microextraction of chlorobenzenes from water samples.

PubMed

Vidal, Lorena; Psillakis, Elefteria; Domini, Claudia E; Grané, Nuria; Marken, Frank; Canals, Antonio

2007-02-12

A headspace single-drop microextraction (HS-SDME) procedure using room temperature ionic liquid and coupled to high-performance liquid chromatography capable of quantifying trace amounts of chlorobenzenes in environmental water samples is proposed. A Plackett-Burman design for screening was carried out in order to determine the significant experimental conditions affecting the HS-SDME process (namely drop volume, aqueous sample volume, stirring speed, ionic strength, extraction time and temperature), and then a central composite design was used to optimize the significant conditions. The optimum experimental conditions found from this statistical evaluation were: a 5 microL microdrop of 1-butyl-3-methylimidazolium hexafluorophosphate, exposed for 37 min to the headspace of a 10 mL aqueous sample placed in a 15 mL vial, stirred at 1580 rpm at room temperature and containing 30% (w/v) NaCl. The calculated calibration curves gave a high level of linearity for all target analytes with correlation coefficients ranging between 0.9981 and 0.9997. The repeatability of the proposed method, expressed as relative standard deviation, varied between 1.6 and 5.1% (n=5). The limits of detection ranged between 0.102 and 0.203 microg L(-1). Matrix effects upon extraction were evaluated by analysing spiked tap and river water as well as effluent water samples originating from a municipal wastewater treatment plant.

Soft shape-adaptive gripping device made from artificial muscle

NASA Astrophysics Data System (ADS)

Hamburg, E.; Vunder, V.; Johanson, U.; Kaasik, F.; Aabloo, A.

2016-04-01

We report on a multifunctional four-finger gripper for soft robotics, suitable for performing delicate manipulation tasks. The gripping device is comprised of separately driven gripping and lifting mechanisms, both made from a separate single piece of smart material - ionic capacitive laminate (ICL) also known as artificial muscle. Compared to other similar devices the relatively high force output of the ICL material allows one to construct a device able to grab and lift objects exceeding multiple times its own weight. Due to flexible design of ICL grips, the device is able to adapt the complex shapes of different objects and allows grasping single or multiple objects simultaneously without damage. The performance of the gripper is evaluated in two different configurations: a) the ultimate grasping strength of the gripping hand; and b) the maximum lifting force of the lifting actuator. The ICL is composed of three main layers: a porous membrane consisting of non-ionic polymer poly(vinylidene fluoride-co-hexafluoropropene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium trifluoromethane-sulfonate (EMITFS), and a reinforcing layer of woven fiberglass cloth. Both sides of the membrane are coated with a carbonaceous electrode. The electrodes are additionally covered with thin gold layers, serving as current collectors. Device made of this material operates silently, requires low driving voltage (<3 V), and is suitable for performing tasks in open air environment.

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).

Ionizing Collisions of Electrons with Radical Species OH, H2 O2 and HO2; Theoretical Calculations

NASA Astrophysics Data System (ADS)

Joshipura, K. N.; Pandya, S. H.; Vaishnav, B. G.; Patel, U. R.

2016-05-01

In this paper we present our calculated total ionization cross sections (TICS) of electron impact on radical targets OH, H2 O2 and HO2 at energies from threshold to 2000 eV. Reactive species such as these pose difficulties in measurements of electron scattering cross sections. No measured data have been reported in this regard except an isolated TICS measurement on OH radical, and hence the present work on the title radicals hold significance. These radical species are present in an environment in which water molecules undergo dissociation (neutral or ionic) in interactions with photons or electrons. The embedding environments could be quite diverse, ranging from our atmosphere to membranes of living cells. Ionization of OH, H2 O2 or HO2 can give rise to further chemistry in the relevant bulk medium. Therefore, it is appropriate and meaningful to examine electron impact ionization of these radicals in comparison with that of water molecules, for which accurate da are available. For the OH target single-centre scattering calculations are performed by starting with a 4-term complex potential, that describes simultaneous elastic plus inelastic scattering. TICS are obtained from the total inelastic cross sections in the complex scattering potential - ionization contribution formalism , a well established method. For H2 O2 and HO2 targets, we employ the additivity rule with overlap or screening corrections. Detailed results will be presented in the Conference.

Poisson-Nernst-Planck Equations for Simulating Biomolecular Diffusion-Reaction Processes II: Size Effects on Ionic Distributions and Diffusion-Reaction Rates

PubMed Central

Lu, Benzhuo; Zhou, Y.C.

2011-01-01

The effects of finite particle size on electrostatics, density profiles, and diffusion have been a long existing topic in the study of ionic solution. The previous size-modified Poisson-Boltzmann and Poisson-Nernst-Planck models are revisited in this article. In contrast to many previous works that can only treat particle species with a single uniform size or two sizes, we generalize the Borukhov model to obtain a size-modified Poisson-Nernst-Planck (SMPNP) model that is able to treat nonuniform particle sizes. The numerical tractability of the model is demonstrated as well. The main contributions of this study are as follows. 1), We show that an (arbitrarily) size-modified PB model is indeed implied by the SMPNP equations under certain boundary/interface conditions, and can be reproduced through numerical solutions of the SMPNP. 2), The size effects in the SMPNP effectively reduce the densities of highly concentrated counterions around the biomolecule. 3), The SMPNP is applied to the diffusion-reaction process for the first time, to our knowledge. In the case of low substrate density near the enzyme reactive site, it is observed that the rate coefficients predicted by SMPNP model are considerably larger than those by the PNP model, suggesting both ions and substrates are subject to finite size effects. 4), An accurate finite element method and a convergent Gummel iteration are developed for the numerical solution of the completely coupled nonlinear system of SMPNP equations. PMID:21575582

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.

Amino acid ionic liquids.

PubMed

Ohno, Hiroyuki; Fukumoto, Kenta

2007-11-01

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.

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.

Design of functional guanidinium ionic liquid aqueous two-phase systems for the efficient purification of protein.

PubMed

Ding, Xueqin; Wang, Yuzhi; Zeng, Qun; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2014-03-07

A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been devised and synthesized based on 1,1,3,3-tetramethylguanidine. The structures of the ionic liquids (ILs) were confirmed by (1)H nuclear magnetic resonance ((1)H NMR) and 13C nuclear magnetic resonance (13C NMR) and the production yields were all above 90%. Functional guanidinium ionic liquid aqueous two-phase systems (FGIL-ATPSs) have been first designed with these functional guanidinium ILs and phosphate solution for the purification of protein. After phase separation, proteins had transferred into the IL-rich phase and the concentrations of proteins were determined by measuring the absorbance at 278 nm using an ultra violet visible (UV-vis) spectrophotometer. The advantages of FGIL-ATPSs were compared with ordinary ionic liquid aqueous two-phase systems (IL-ATPSs). The proposed FGIL-ATPS has been applied to purify lysozyme, trypsin, ovalbumin and bovine serum albumin. Single factor experiments were used to research the effects of the process, such as the amount of ionic liquid (IL), the concentration of salt solution, temperature and the amount of protein. The purification efficiency reaches to 97.05%. The secondary structure of protein during the experimental process was observed upon investigation using UV-vis spectrophotometer, Fourier-transform infrared spectroscopy (FT-IR) and circular dichroism spectrum (CD spectrum). The precision, stability and repeatability of the process were investigated. The mechanisms of purification were researched by dynamic light scattering (DLS), determination of the conductivity and transmission electron microscopy (TEM). It was suggested that aggregation and embrace phenomenon play a significant role in the purification of proteins. All the results show that FGIL-ATPSs have huge potential to offer new possibility in the purification of proteins. Copyright © 2014 Elsevier B.V. All rights reserved.

Co-transport of gold nanospheres with single-walled carbon nanotubes in saturated porous media.

PubMed

Afrooz, A R M Nabiul; Das, Dipesh; Murphy, Catherine J; Vikesland, Peter; Saleh, Navid B

2016-08-01

Porous media transport of engineered nanomaterials (ENMs) is typically assessed in a controlled single-particulate environment. Presence of a secondary particle (either natural or engineered) in the natural environment though likely, is rarely taken into consideration in assessing ENMs' transport behavior. This study systematically assesses the effect of a secondary ENM (i.e., pluronic acid modified single-walled carbon nanotubes, PA-SWNTs) on a primary particle (i.e., gold nanospheres, AuNSs) transport through saturated porous media under a wide range of aquatic conditions (1-100 mM NaCl). AuNS hetero-dispersions (i.e., with PA-SWNTs) are transported through saturated sand columns, and the transport behavior is compared to AuNS-only homo-dispersion cases, which display classical ionic strength-dependent behavior. AuNS hetero-dispersion, however, is highly mobile with little to no ionic strength-dependent effects. This study also assesses the role of pre-coating of the collectors with PA-SWNTs on AuNSs' mobility, thereby elucidating the role played by the order of introduction of the secondary particles. Pre-existence of the secondary particles in the porous media shows enhanced filtration of primary AuNSs. However, the presence of natural organic matter (NOM) slightly increases AuNS mobility through PA-SWNT coated sand at 10 mM ionic strength. The study results demonstrate that the presence and order of addition of the secondary particles strongly influence primary particles' mobility. Thus ENMs can demonstrate facilitated transport or enhanced removal, depending on the presence of the secondary particulate matter and background solution chemistry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reduction of toxic Cr(VI)-humic acid in an ionic liquid

NASA Astrophysics Data System (ADS)

Huang, Hsin-Liang; Huang, Hsin-Hung; Wei, Yu Jhe

2017-07-01

Remediation of soil contaminated by toxic hexavalent chromium species associated with humic acid (Cr(VI)-HA) and absorbed Cr(VI) in pores frequently experiences technical difficulties. In the present work, a feasibility study for extraction of the Cr(VI) species from a molecular sieve MCM-41 (Mobil Composition of Matter No. 41) that was used to simulate the pore system of soil, with a green solvent (ionic liquid), 1-butyl-3-methylimidazolium chloride ([C4mim][Cl]), was carried out. After a 30-min extraction, approximately 70% of the Cr(VI) species can be extracted. By component fitted X-ray absorption near edge structure (XANES) spectroscopy, about 48% of the Cr(VI)-HA are reduced to form less toxic species (Cr(III)-HA) during extraction with [C4mim][Cl]. Note that the Cr-O in the [C4mim][Cl] phase has a slightly greater bond distance (BD) (0.162 nm) possibly due to the fact of that the fraction of Cr(III) is increased in the extraction process. The non-extractable chromium remaining in MCM-41 has a much greater fraction of Cr(III) (78%) and its BD is further increased to 0.195 nm. The coordination numbers of chromium for the 1st shell Cr-O in the Cr(VI) and Cr(III) species are in the range of 2.4-2.9, suggesting that chromium is chelated with HA and adsorbed in MCM-41. The 1H NMR data also suggest that the enhanced reduction of the Cr(VI) species may be related to interactions between chromium species and electron-rich imidazole ring of the [C4mim]+. This work also exemplifies that the fate of toxic chromium species in the complicated remediation of contaminated soils can be revealed in a molecule-scale study by synchrotron X-ray absorption spectroscopy.

Variation of the interphase heterochromatin in Artemia (Crustacea, Anostraca) of the Americas is related to changes in nuclear size and ionic composition of hipersaline habitats.

PubMed

Parraguez, M; Gajardo, G

2017-01-01

The populations of Artemia (or brine shrimp) from the Americas exhibit a wide variation in the amount of interphase heterochromatin. There is interest in understanding how this variation affects different parameters, from the cellular to the organismal levels. This should help to clarify the ability of this organism to tolerate brine habitats regularly subject to strong abiotic changes. In this study, we assessed the amount of interphase heterochromatin per nucleus based on chromocenter number (N-CHR) and relative area of chromocenter (R-CHR) in two species of Artemia, A. franciscana (Kellog, 1906) (n=9 populations) and A. persimilis (Piccinelli and Prosdocimi, 1968) (n=3 populations), to investigate the effect on nuclear size (S-NUC). The relationship of the R-CHR parameter with the ionic composition (IC) of brine habitats was also analysed. Our results indicate a significant variation in the amount of heterochromatin both within and between species (ANOVA, p<0.001). The heterochromatin varied from 0.81 ± 1.17 to 12.58 ± 3.78 and from 0.19 ± 0.34% to 11.78 ± 3.71% across all populations, for N-CHR and R-CHR parameters, respectively. N-CHR showed less variation than R-CHR (variation index 15.5-fold vs. 62-fold). At least five populations showed a significant association (p<0.05) between R-CHR and S-NUC, either with negative (four populations, r= from -0.643 to -0.443), or positive (one population, r= 0.367) values.Within each species, there were no significant associations between both parameters (p>0.05). The R-CHR and IC parameters were associated significantly for the magnesium ion (r= 0.496, p<0.05) and also for the chloride, sodium and calcium ions (r = from -0.705 to -0.478, p<0.05). At species level, a significant association between both parameters was also found in A. franciscana populations, for the sulphate and calcium ions, in contrast to A. persimilis. These findings suggest that the amount of interphase heterochromatin modifies the nuclear size in Artemia. Our data also indicate that change in the amount of interphase heterochromatin is in line with the ionic composition of brines. This would be a species-specific phenomenon, whose occurrence may be involved in the ability of this organism to survive in these environments.

Geometry effect on electrokinetic flow and ionic conductance in pH-regulated nanochannels

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Moosavi, Ali; Sadeghi, Arman

2017-12-01

Semi-analytical solutions are obtained for the electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties associated with long pH-regulated nanochannels of arbitrary but constant cross-sectional area. The effects of electric double layer overlap, multiple ionic species, and surface association/dissociation reactions are all taken into account, assuming low surface potentials. The method of analysis includes series solutions which the pertinent coefficients are obtained by applying the wall boundary conditions using either of the least-squares or point matching techniques. Although the procedure is general enough to be applied to almost any arbitrary cross section, nine nanogeometries including polygonal, trapezoidal, double-trapezoidal, rectangular, elliptical, semi-elliptical, isosceles triangular, rhombic, and isotropically etched profiles are selected for presentation. For the special case of an elliptic cross section, full analytical solutions are also obtained utilizing the Mathieu functions. We show that the geometrical configuration plays a key role in determination of the ionic conductance, surface charge density, electrical potential and velocity fields, and proton enhancement. In this respect, the net electric charge and convective ionic conductance are higher for channels of larger perimeter to area ratio, whereas the opposite is true for the average surface charge density and mean velocity; the geometry impact on the two latest ones, however, vanishes if the background salt concentration is high enough. Moreover, we demonstrate that considering a constant surface potential equal to the average charge-regulated potential provides sufficiently accurate results for smooth geometries such as an ellipse at medium-high aspect ratios but leads to significant errors for geometries having narrow corners such as a triangle.

The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community to develop innovative ways to improve energy storage and find more efficient methods of transporting the energy. Polymers containing charged species that show high ionic conductivity and good mechanical integrity are the essential components of these energy storage and transport systems. In this talk, first, I will present a fundamental understanding of the thermodynamics and transport in ion-containing block copolymers with a focus on the structure-property relationships. Tailoring the intermolecular interactions between the polymer matrix and the embedded charges appeared to be vital for controlling the transport properties. Particularly, the achievement of well-defined self-assembled morphologies with three-dimensional symmetries has proven to facilitate fast ion transport by constructing less tortuous ion-conducting pathways. Examples of attained morphologies include disorder, lamellae, gyroid, Fddd, hexagonal cylinder, body-centered cubic, face-centered cubic, and A15 phases. Second, various strategies for accessing high cation transference number as well as improved ionic conductivity from ionic-containing polymers are enclosed; (1) the inclusion of terminal ionic units as a new means to control the nanoscale morphologies and the transport efficiency of block copolymer electrolytes and (2) the addition of zwitterions that offered a polar medium close to water, and accordingly increased the charge density and ionic conductivity. The obtained knowledge on polymer electrolytes could be used in a wide range of emerging nanotechnologies such as fuel cells, lithium batteries, and electro-active actuators.

Ionic and viscoelastic mechanisms of a bucky-gel actuator

NASA Astrophysics Data System (ADS)

Kruusamäe, Karl; Sugino, Takushi; Asaka, Kinji

2015-07-01

Ionic electromechanically active polymers (IEAPs) are considered attractive candidates for soft, miniature, and lightweight actuators. The bucky-gel actuator is a carbonaceous subtype of IEAP that due to its structure (i.e. two highly porous electrodes sandwiching a thin ion-permeable electrolyte layer) and composition (i.e. being composed of soft porous polymer, carbon nanotubes, and ionic liquid) is very similar to an electric double-layer capacitor. In response to the voltage applied between the electrodes of a bucky-gel actuator, the laminar structure bends. The time domain behavior exhibits, however, a phenomenon called the back-relaxation, i.e., after some time the direction of bending is reversed even though voltage remains constant. In spite of the working mechanism of IEAP actuators being generally attributed to the transport of ions within the soft multilayer system, the specific details remain unclear. A so-called two-carrier model proposes that the bending and subsequent back-relaxation are caused by the relocation of two ionic species having different mobilities as they enter and exit the electrode layers. By adopting the two-carrier model for bucky-gel actuators, we see very good agreement between the mathematical representation and the experimental data of the electromechanical behavior. Furthermore, since the bucky-gel actuator is viscoelastic, we propose to use the time domain response of a blocking force as the key parameter related to the inner ionic mechanism. We also introduce a method to estimate the viscoelastic creep compliance function from the time domain responses for curvature and blocking force. This analysis includes four types of bucky-gel actuators of varying composition and structure.

Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density.

PubMed

Cheng, Qian; Tang, Jie; Ma, Jun; Zhang, Han; Shinya, Norio; Qin, Lu-Chang

2011-10-21

We describe a graphene and single-walled carbon nanotube (SWCNT) composite film prepared by a blending process for use as electrodes in high energy density supercapacitors. Specific capacitances of 290.6 F g(-1) and 201.0 F g(-1) have been obtained for a single electrode in aqueous and organic electrolytes, respectively, using a more practical two-electrode testing system. In the organic electrolyte the energy density reached 62.8 Wh kg(-1) and the power density reached 58.5 kW kg(-1). The addition of single-walled carbon nanotubes raised the energy density by 23% and power density by 31% more than the graphene electrodes. The graphene/CNT electrodes exhibited an ultra-high energy density of 155.6 Wh kg(-1) in ionic liquid at room temperature. In addition, the specific capacitance increased by 29% after 1000 cycles in ionic liquid, indicating their excellent cyclicity. The SWCNTs acted as a conductive additive, spacer, and binder in the graphene/CNT supercapacitors. This work suggests that our graphene/CNT supercapacitors can be comparable to NiMH batteries in performance and are promising for applications in hybrid vehicles and electric vehicles. This journal is © the Owner Societies 2011

Ca2+ and MgATP2- dependence of shortening in skinned single smooth muscle cells.

PubMed

Warshaw, D M; McBride, W J; Hubbard, M S

1987-04-01

Most studies of skinned smooth muscle have been performed in whole tissue preparations. In this study, we report the development of a chemically skinned single smooth muscle cell preparation from the toad, Bufo marinus, stomach. Isolated smooth muscle cells were skinned using saponin. The effect of various ionic environments (i.e., changing free Ca2+ and MgATP2-) on skinned cell contractile response was assessed by measuring cell lengths from populations of cells using a computer-assisted length-measuring system. Comparison of cell length histograms were used to determine the extent of cell shortening in response to a given ionic perturbation. Once skinned, the single cells shortened with a sensitivity to free calcium (ED50 = 1.5 microM Ca2+) that was three orders of magnitude lower than potassium depolarized cells (ED50 = 1.5 mM Ca2+). In addition to the calcium sensitivity, the effect of free MgATP2- on the extent of cell shortening was investigated. The extent of cell shortening was dependent on free MgATP2- with the maximum shortening response occurring at MgATP2- greater than 1 mM.

Electrophoretic separations in poly(dimethylsiloxane) microchips using a mixture of ionic and zwitterionic surfactants

PubMed Central

Guan, Qian; Noblitt, Scott D.; Henry, Charles S.

2012-01-01

The use of mixtures of ionic and zwitterionic surfactants in poly(dimethylsiloxane) (PDMS) microchips is reported. The effect of surfactant concentration on EOF was studied for a single anionic surfactant (sodium dodecyl sulfate, SDS), a single zwitterionic surfactant (N-tetradecylammonium-N,N-dimethyl-3-ammonio-1-propanesulfonate, TDAPS), and a mixed SDS/TDAPS surfactant system. SDS increased the EOF as reported previously while TDAPS showed an initial increase in EOF followed by a reduction at higher concentrations. When TDAPS was added to a solution containing SDS, the EOF decreased in a concentration dependent manner. The EOF for all three surfactant systems followed expected pH trends, with increasing EOF at higher pH. The mixed surfactant system allowed tuning of the EOF across a range of pH and concentration conditions. After establishing the EOF behavior, the adsorption/desorption kinetics were measured and showed a slower adsorption/desorption rate for TDAPS than SDS. Finally, the separation and electrochemical detection of model catecholamines in buffer and reduced glutathione (GSH) in red blood cell lysate using the mixed surfactant system were explored. The mixed surfactant system provided shorter analysis times and/or improved resolution when compared to the single surfactant systems. PMID:22222982

Electron Phonon Coupling versus Photoelectron Energy Loss at the Origin of Replica Bands in Photoemission of FeSe on SrTiO3

NASA Astrophysics Data System (ADS)

Li, Fengmiao; Sawatzky, George A.

2018-06-01

The recent observation of replica bands in single-layer FeSe /SrTiO3 by angle-resolved photoemission spectroscopy (ARPES) has triggered intense discussions concerning the potential influence of the FeSe electrons coupling with substrate phonons on the superconducting transition temperature. Here we provide strong evidence that the replica bands observed in the single-layer FeSe /SrTiO3 system and several other cases are largely due to the energy loss processes of the escaping photoelectron, resulted from the well-known strong coupling of external propagating electrons to Fuchs-Kliewer surface phonons in ionic materials in general. The photoelectron energy loss in ARPES on single-layer FeSe /SrTiO3 is calculated using the demonstrated successful semiclassical dielectric theory in describing low energy electron energy loss spectroscopy of ionic insulators. Our result shows that the observed replica bands are mostly a result of extrinsic photoelectron energy loss and not a result of the electron phonon interaction of the Fe d electrons with the substrate phonons. The strong enhancement of the superconducting transition temperature in these monolayers remains an open question.

Point defects at the ice (0001) surface

PubMed Central

Watkins, Matthew; VandeVondele, Joost; Slater, Ben

2010-01-01

Using density functional theory we investigate whether intrinsic defects in ice surface segregate. We predict that hydronium, hydroxide, and the Bjerrum L- and D-defects are all more stable at the surface. However, the energetic cost to create a D-defect at the surface and migrate it into the bulk crystal is smaller than its bulk formation energy. Absolute and relative segregation energies are sensitive to the surface structure of ice, especially the spatial distribution of protons associated with dangling hydrogen bonds. It is found that the basal plane surface of hexagonal ice increases the bulk concentration of Bjerrum defects, strongly favoring D-defects over L-defects. Dangling protons associated with undercoordinated water molecules are preferentially injected into the crystal bulk as Bjerrum D-defects, leading to a surface dipole that attracts hydronium ions. Aside from the disparity in segregation energies for the Bjerrum defects, we find the interactions between defect species to be very finely balanced; surface segregation energies for hydronium and hydroxide species and trapping energies of these ionic species with Bjerrum defects are equal within the accuracy of our calculations. The mobility of the ionic hydronium and hydroxide species is greatly reduced at the surface in comparison to the bulk due to surface sites with high trapping affinities. We suggest that, in pure ice samples, the surface of ice will have an acidic character due to the presence of hydronium ions. This may be important in understanding the reactivity of ice particulates in the upper atmosphere and at the boundary layer. PMID:20615938

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.

Highly stable gel electrolytes for dye solar cells based on chemically engineered polymethacrylic hosts.

PubMed

De Gregorio, Gian Luca; Agosta, Rita; Giannuzzi, Roberto; Martina, Francesca; De Marco, Luisa; Manca, Michele; Gigli, Giuseppe

2012-03-25

Four different species of ionically conductive polymers were synthesized and successfully implemented to formulate novel quasi-solid electrolytes for dye solar cells. A power conversion efficiency superior to 85% of the correspondent liquid electrolyte as well as an excellent cell's stability was demonstrated after 500 days of storage.

Ab initio quantum chemical calculations of the interaction between radioactive elements and imidazolium based ionic liquids

NASA Astrophysics Data System (ADS)

Saravanan, A. V. Sai; Abishek, B.; Anantharaj, R.

2018-04-01

The fundamental natures of the molecular level interaction and charge transfer between specific radioactive elements and ionic liquids of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[NTf2]-), 1-Butyl-3-methylimidazolium ethylsulfate ([BMIM]+[ES]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]+[BF4]-) were investigated utilising HF theory and B3LYP hybrid DFT. The ambiguity in reaction mechanism of the interacting species dictates to employ Effective Core Potential (ECP) basis sets such as UGBS, SDD, and SDDAll to account for the relativistic effects of deep core electrons in the system involving potential, heavy and hazardous radioactive elements present in nuclear waste. The SCF energy convergence of each system validates the characterisation of the molecular orbitals as a linear combination of atomic orbitals utilising fixed MO coefficients and the optimized geometry of each system is visualised based on which Mulliken partial charge analysis is carried out to account for the polarising behaviour of the radioactive element and charge transfer between the IL phase by comparison with the bare IL species.

Ultrafiltration by a compacted clay membrane-II. Sodium ion exclusion at various ionic strengths

USGS Publications Warehouse

Hanshaw, B.B.; Coplen, T.B.

1973-01-01

Several recent laboratory studies and field investigations have indicated that shales and compacted clay minerals behave as semipermeable membranes. One of the properties of semipermeable membranes is to retard or prevent the passage of charged ionic species through the membrane pores while allowing relatively free movement of uncharged species. This phenomenon is termed salt filtering, reverse osmosis, or ultrafiltration. This paper shows how one can proceed from the ion exchange capacity of clay minerals and, by means of Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane. Reasonable agreement between theory and laboratory results were found. The concentration of the ultrafiltrate was always greater than predicted because of uncertainty in values of some parameters in the equations. Ultrafiltration phenomena may be responsible for the formation of some subsurface brines and mineral deposits. The effect should also be taken into consideration in any proposal for subsurface waste emplacement in an environment containing large quantities of clay minerals. ?? 1973.

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]-.

Fundamentals of ionic conductivity relaxation gained from study of procaine hydrochloride and procainamide hydrochloride at ambient and elevated pressure.

PubMed

Wojnarowska, Z; Swiety-Pospiech, A; Grzybowska, K; Hawelek, L; Paluch, M; Ngai, K L

2012-04-28

The pharmaceuticals, procaine hydrochloride and procainamide hydrochloride, are glass-forming as well as ionically conducting materials. We have made dielectric measurements at ambient and elevated pressures to characterize the dynamics of the ion conductivity relaxation in these pharmaceuticals, and calorimetric measurements for the structural relaxation. Perhaps due to their special chemical and physical structures, novel features are found in the ionic conductivity relaxation of these pharmaceuticals. Data of conductivity relaxation in most ionic conductors when represented by the electric loss modulus usually show a single resolved peak in the electric modulus loss M(")(f) spectra. However, in procaine hydrochloride and procainamide hydrochloride we find in addition another resolved loss peak at higher frequencies over a temperature range spanning across T(g). The situation is analogous to many non-ionic glass-formers showing the presence of the structural α-relaxation together with the Johari-Goldstein (JG) β-relaxation. Naturally the analogy leads us to name the slower and faster processes resolved in procaine hydrochloride and procainamide hydrochloride as the primary α-conductivity relaxation and the secondary β-conductivity relaxation, respectively. The analogy of the β-conductivity relaxation in procaine HCl and procainamide HCl with JG β-relaxation in non-ionic glass-formers goes further by the finding that the β-conductivity is strongly related to the α-conductivity relaxation at temperatures above and below T(g). At elevated pressure but compensated by raising temperature to maintain α-conductivity relaxation time constant, the data show invariance of the ratio between the β- and the α-conductivity relaxation times to changes of thermodynamic condition. This property indicates that the β-conductivity relaxation has fundamental importance and is indispensable as the precursor of the α-conductivity relaxation, analogous to the relation found between the Johari-Goldstein β-relaxation and the structural α-relaxation in non-ionic glass-forming systems. The novel features of the ionic conductivity relaxation are brought out by presenting the measurements in terms of the electric modulus or permittivity. If presented in terms of conductivity, the novel features are lost. This warns against insisting that a log-log plot of conductivity vs. frequency is optimal to reveal and interpret the dynamics of ionic conductors.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

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

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

Discrimination among individual Watson–Crick base pairs at the termini of single DNA hairpin molecules

PubMed Central

Vercoutere, Wenonah A.; Winters-Hilt, Stephen; DeGuzman, Veronica S.; Deamer, David; Ridino, Sam E.; Rodgers, Joseph T.; Olsen, Hugh E.; Marziali, Andre; Akeson, Mark

2003-01-01

Nanoscale α-hemolysin pores can be used to analyze individual DNA or RNA molecules. Serial examination of hundreds to thousands of molecules per minute is possible using ionic current impedance as the measured property. In a recent report, we showed that a nanopore device coupled with machine learning algorithms could automatically discriminate among the four combinations of Watson–Crick base pairs and their orientations at the ends of individual DNA hairpin molecules. Here we use kinetic analysis to demonstrate that ionic current signatures caused by these hairpin molecules depend on the number of hydrogen bonds within the terminal base pair, stacking between the terminal base pair and its nearest neighbor, and 5′ versus 3′ orientation of the terminal bases independent of their nearest neighbors. This report constitutes evidence that single Watson–Crick base pairs can be identified within individual unmodified DNA hairpin molecules based on their dynamic behavior in a nanoscale pore. PMID:12582251

One-volt-driven superfast polymer actuators based on single-ion conductors

PubMed Central

Kim, Onnuri; Kim, Hoon; Choi, U. Hyeok; Park, Moon Jeong

2016-01-01

The key challenges in the advancement of actuator technologies related to artificial muscles include fast-response time, low operation voltages and durability. Although several researchers have tackled these challenges over the last few decades, no breakthrough has been made. Here we describe a platform for the development of soft actuators that moves a few millimetres under 1 V in air, with a superfast response time of tens of milliseconds. An essential component of this actuator is the single-ion-conducting polymers that contain well-defined ionic domains through the introduction of zwitterions; this achieved an exceptionally high dielectric constant of 76 and a 300-fold enhancement in ionic conductivity. Moreover, the actuator demonstrated long-term durability, with negligible changes in the actuator stroke over 20,000 cycles in air. Owing to its low-power consumption (only 4 mW), we believe that this actuator could pave the way for cutting-edge biomimetic technologies in the future. PMID:27857067

Organic electrical double layer transistors gated with ionic liquids

NASA Astrophysics Data System (ADS)

Xie, Wei; Frisbie, C. Daniel

2011-03-01

Transport in organic semiconductors gated with several types of ionic liquids has been systematically studied at charge densities larger than 1013 cm-2 . We observe a pronounced maximum in channel conductance for both p-type and n-type organic single crystals which is attributed to carrier localization at the semiconductor-electrolyte interface. Carrier mobility, as well as charge density and dielectric capacitance are determined through displacement current measurement and capacitance-voltage measurement. By using a larger-sized and spherical anion, tris(pentafluoroethyl)trifluorophosphate (FAP), effective carrier mobility in rubrene can be enhanced substantially up to 3.2 cm2 V-1 s -1 . Efforts have been made to maximize the charge density in rubrene single crystals, and at low temperature when higher gate bias can be applied, charge density can more than double the amount of that at room temperature, reaching 8*1013 cm-2 holes (0.4 holes per rubrene molecule). NSF MRSEC program at the University of Minnesota.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

DOE PAGES

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne

2015-11-24

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D 2-tagged GlyGlyH +·(H 2O) 1–4 are presented. As a result, they display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

Phase Behavior of a Single Structured Ionomer Chain in Solution

DOE PAGES

Aryal, Dipak; Etampawala, Thusitha; Perahia, Dvora; ...

2014-08-14

Structured polymers offer a means to tailor transport pathways within mechanically stable manifolds. Here we examine the building block of such a membrane, namely a single large pentablock co-polymer that consist of a center block of a randomly sulfonated polystyrene, designed for transport, tethered to poly-ethylene-r-propylene and end-capped by poly-t-butyl styrene, for mechanical stability,using molecular dynamics simulations. The polymer structure in a cyclohexane-heptane mixture, a technologically viable solvent, and in water, a poor solvent for all segments and a ubiquitous substance is extracted. In all solvents the pentablock collapsed into nearly spherical aggregates where the ionic block is segregated. Inmore » hydrophobic solvents, the ionic block resides in the center, surrounded by swollen intermix of flexible and end blocks. In water all blocks are collapsed with the sulfonated block residing on the surface. Our results demonstrate that solvents drive different local nano-segregation, providing a gateway to assemble membranes with controlled topology.« less

The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration.

PubMed

Smith, Alexander M; Lee, Alpha A; Perkin, Susan

2016-06-16

According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye-Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied-including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids-collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.

Extension of nanoconfined DNA: Quantitative comparison between experiment and theory

NASA Astrophysics Data System (ADS)

Iarko, V.; Werner, E.; Nyberg, L. K.; Müller, V.; Fritzsche, J.; Ambjörnsson, T.; Beech, J. P.; Tegenfeldt, J. O.; Mehlig, K.; Westerlund, F.; Mehlig, B.

2015-12-01

The extension of DNA confined to nanochannels has been studied intensively and in detail. However, quantitative comparisons between experiments and model calculations are difficult because most theoretical predictions involve undetermined prefactors, and because the model parameters (contour length, Kuhn length, effective width) are difficult to compute reliably, leading to substantial uncertainties. Here we use a recent asymptotically exact theory for the DNA extension in the "extended de Gennes regime" that allows us to compare experimental results with theory. For this purpose, we performed experiments measuring the mean DNA extension and its standard deviation while varying the channel geometry, dye intercalation ratio, and ionic strength of the buffer. The experimental results agree very well with theory at high ionic strengths, indicating that the model parameters are reliable. At low ionic strengths, the agreement is less good. We discuss possible reasons. In principle, our approach allows us to measure the Kuhn length and the effective width of a single DNA molecule and more generally of semiflexible polymers in solution.

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.

Exploring low-temperature dehydrogenation at ionic Cu sites in beta zeolite to enable alkane recycle in dimethyl ether homologation

DOE PAGES

Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah; ...

2017-04-24

Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Bronsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. Furthermore, these results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C 5+) hydrocarbon yield.

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.

Dopant selection for control of charge carrier density and mobility in amorphous indium oxide thin-film transistors: Comparison between Si- and W-dopants

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

Mitoma, Nobuhiko, E-mail: MITOMA.Nobuhiko@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Kizu, Takio; Lin, Meng-Fang

The dependence of oxygen vacancy suppression on dopant species in amorphous indium oxide (a-InO{sub x}) thin film transistors (TFTs) is reported. In a-InO{sub x} TFTs incorporating equivalent atom densities of Si- and W-dopants, absorption of oxygen in the host a-InO{sub x} matrix was found to depend on difference of Gibbs free energy of the dopants for oxidation. For fully oxidized films, the extracted channel conductivity was higher in the a-InO{sub x} TFTs containing dopants of small ionic radius. This can be explained by a reduction in the ionic scattering cross sectional area caused by charge screening effects.

Training and shape retention in conducting polymer artificial muscles

NASA Astrophysics Data System (ADS)

Tominaga, Kazuo; Hashimoto, Hikaru; Takashima, Wataru; Kaneto, Keiichi

2011-12-01

Electrochemomechanical deformation (ECMD) of the conducting polymer polyaniline film is studied to investigate the behaviour of actuation under tensile loads. The ECMD was induced by the strains due to the insertion of ionic species (cyclic strain) and a creep due to applied loads during the redox cycle. The cyclic strain was enhanced by the experience of high tensile loads, indicating a training effect. The training effect was explained by the enhanced electrochemical activity of the film. The creep was recovered by removal of the tensile load and several electrochemical cycles. This fact indicates that the creep results from the one-dimensional anisotropic deformation, and is retained (shape retention) by the ionic crosslink. The recovery of creep results from the elastic relaxation of the polymer conformation.

Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures.

PubMed

Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Mei-Hsiu; Chen, Ting-Chien; Ma, Sen-Yi

2007-10-01

A pyrolysis method was employed to recycle the metals and brominated compounds blended into printed circuit boards. This research investigated the effect of particle size and process temperature on the element composition of IC boards and pyrolytic residues, liquid products, and water-soluble ionic species in the exhaust, with the overall goal being to identify the pyrolysis conditions that will have the least impact on the environment. Integrated circuit (IC) boards were crushed into 5-40 mesh (0.71-4.4mm), and the crushed particles were pyrolyzed at temperatures ranging from 200 to 500 degrees C. The thermal decomposition kinetics were measured by a thermogravimetric (TG) analyzer. The composition of pyrolytic residues was analyzed by Energy Dispersive X-ray Spectrometer (EDS), Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In addition, the element compositions of liquid products were analyzed by ICP-AES and ICP-MS. Pyrolytic exhaust was collected by a water-absorption system in an ice-bath cooler, and IC analysis showed that the absorbed solution comprised 11 ionic species. Based on the pyrolytic kinetic parameters of TG analysis and pyrolytic residues at various temperatures for 30 min, the effect of particle size was insignificant in this study, and temperature was the key factor for the IC board pyrolysis. Two stages of decomposition were found for IC board pyrolysis under nitrogen atmosphere. The activation energy was 38-47 kcal/mol for the first-stage reaction and 5.2-9.4 kcal/mol for the second-stage reaction. Metal content was low in the liquid by-product of the IC board pyrolysis process, which is an advantage in that the liquid product could be used as a fuel. Brominate and ammonium were the main water-soluble ionic species of the pyrolytic exhaust. A plan for their safe and effective disposal must be developed if the pyrolytic recycling process is to be applied to IC boards.

Speciation of chromium compounds from humic acid-zeolite Y to an ionic liquid during extraction.

PubMed

Huang, Hsin-Liang; Wei, Yu Jhe

2018-03-01

By synchrotron X-ray absorption spectroscopy, chemical structures of hexavalent chromium (Cr(VI))/trivalent chromium (Cr(III)) adsorbed on humic acid (HA)-zeolite Y and extracted in an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate ([C 4 mim][BF 4 ])) have been studied. By combining the competitive adsorption results and reduction of Cr(VI)-HA with the carboxyl groups of HA, Cr(III)-HA (58%) was shown to be the major compound in HA-zeolite Y using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy. In an ionic liquid phase, the reduction of Cr(VI)-HA to Cr(III)-HA and the desorption of Cr(III) from HA were caused by [C 4 mim][BF 4 ]. The 9 F nuclear magnetic resonance (NMR) spectra show that the perturbation of the [C 4 mim][BF 4 ] anion was affected by the extractable chromium species. The formation of a Cr(III) ion affected the increase in the bond distance for the 1st shell CrO of the chromium species in [C 4 mim][BF 4 ] using extended X-ray absorption fine structure (EXAFS) spectroscopy. The changes in the non-extractable chromium species remaining in HA-zeolite Y were also caused by [C 4 mim][BF 4 ] during extraction. The desorption of the absorbed Cr(III) on HA and zeolite Y was observed to form Cr(III) ions. As the percentage of Cr(III) ions remaining in HA-zeolite Y increased, a slightly greater bond distance for CrO was found at 2.01 Å. The enhanced reduction of Cr(VI)-HA and desorption of Cr(III) adsorbed on the HA and zeolite Y to form Cr(III) ions were affected by [C 4 mim][BF 4 ]. Increased mobility of Cr(III) in the simulated soil can promote the migration of Cr(III) ions into the H 2 O during soil washing for remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Toward the Elucidation of the Competing Role of Evaporation and Thermal Decomposition in Ionic Liquids: A Multitechnique Study of the Vaporization Behavior of 1-Butyl-3-methylimidazolium Hexafluorophosphate under Effusion Conditions.

PubMed

Volpe, V; Brunetti, B; Gigli, G; Lapi, A; Vecchio Ciprioti, S; Ciccioli, A

2017-11-16

The evaporation/decomposition behavior of the imidazolium ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF 6 ) was investigated in the overall temperature range 425-551 K by means of the molecular-effusion-based techniques Knudsen effusion mass loss (KEML) and Knudsen effusion mass spectrometry (KEMS), using effusion orifices of different size (from 0.2 to 3 mm in diameter). Specific effusion fluxes measured by KEML were found to depend markedly on the orifice size, suggesting the occurrence of a kinetically delayed evaporation/decomposition process. KEMS experiments revealed that other species are present in the vapor phase besides the intact ion pair BMImPF 6 (g) produced by the simple evaporation BMImPF 6 (l) = BMImPF 6 (g), with relative abundances depending on the orifice size-the larger the orifice, the larger the contribution of the BMImPF 6 (g) species. By combining KEML and KEMS results, the conclusion is drawn that in the investigated temperature range, when small effusion orifices are used, a significant part of the mass loss/volatility of BMImPF 6 is due to molecular products formed by decomposition/dissociation processes rather than to evaporated intact ion pairs. Additional experiments performed by nonisothermal thermogravimetry-differential thermal analysis (TG-DTA) further support the evidence of simultaneous evaporation/decomposition, although the conventional decomposition temperature derived from TG curves is much higher than the temperatures covered in effusion experiments. Partial pressures of the BMImPF 6 (g) species were derived from KEMS spectra and analyzed by second- and third-law methods giving a value of Δ evap H 298K ° = 145.3 ± 2.9 kJ·mol -1 for the standard evaporation enthalpy of BMImPF 6 . A comparison is done with the behavior of the 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf 2 ) ionic liquid.

Binding thermodynamics of phosphorylated inhibitors to triosephosphate isomerase and the contribution of electrostatic interactions.

PubMed

Serratos, Iris N; Pérez-Hernández, Gerardo; Garza-Ramos, Georgina; Hernández-Arana, Andrés; González-Mondragón, Edith; Zubillaga, Rafael A

2011-01-07

Electrostatic interactions have a central role in some biological processes, such as recognition of charged ligands by proteins. We characterized the binding energetics of yeast triosephosphate isomerase (TIM) with phosphorylated inhibitors 2-phosphoglycollate (2PG) and phosphoglycolohydroxamate (PGH). We determined the thermodynamic parameters of the binding process (K(b), ΔG(b), ΔH(b), ΔS(b) and ΔC(p)) with different concentrations of NaCl, using fluorimetric and calorimetric titrations in the conventional mode of ITC and a novel method, multithermal titration calorimetry (MTC), which enabled us to measure ΔC(p) in a single experiment. We ruled out specific interactions of Na(+) and Cl(-) with the native enzyme and did not detect significant linked protonation effects upon the binding of inhibitors. Increasing ionic strength (I) caused K(b), ΔG(b) and ΔH(b) to become less favorable, while ΔS(b) became less unfavorable. From the variation of K(b) with I, we determined the electrostatic contribution of TIM-2PG and TIM-PGH to ΔG(b) at I=0.06 M and 25 °C to be 36% and 26%, respectively. The greater affinity of PGH for TIM is due to a more favorable ΔH(b) compared to 2PG (by 19-24 kJ mol(-1) at 25 °C). This difference is compatible with PGH establishing up to five more hydrogen bonds with TIM. Both binding ΔC(p)s were negative, and less negative with increasing ionic strength. ΔC(p)s at I=0.06 M were much more negative than predicted by surface area models. Water molecules trapped in the interface when ligands bind to protein could explain the highly negative ΔCps. Thermodynamic binding functions for TIM-2PG changed more with ionic strength than those for TIM-PGH. This greater dependence is consistent with linked, but compensated, protonation equilibriums yielding the dianionic species of 2PG that binds to TIM, process that is not required for PGH. Copyright © 2010 Elsevier Ltd. All rights reserved.

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.

Deviation from Boltzmann distribution in excited energy levels of singly-ionized iron in an argon glow discharge plasma for atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Lei; Kashiwakura, Shunsuke; Wagatsuma, Kazuaki

2012-01-01

A Boltzmann plot for many iron ionic lines having excitation energies of 4.7-9.1 eV was investigated in an argon glow discharge plasma when the discharge parameters, such as the voltage/current and the gas pressure, were varied. A Grimm-style radiation source was employed in a DC voltage range of 400-800 V at argon pressures of 400-930 Pa. The plot did not follow a linear relationship over a wide range of the excitation energy, but it yielded a normal Boltzmann distribution in the range of 4.7-5.8 eV and a large overpopulation in higher-lying excitation levels of iron ion. A probable reason for this phenomenon is that excitations for higher excited energy levels of iron ion would be predominantly caused by non-thermal collisions with argon species, the internal energy of which is received by iron atoms for the ionization. Particular intense ionic lines, which gave a maximum peak of the Boltzmann plot, were observed at an excitation energy of ca. 7.7 eV. They were the Fe II 257.297-nm and the Fe II 258.111-nm lines, derived from the 3d54s4p 6P excited levels. The 3d54s4p 6P excited levels can be highly populated through a resonance charge transfer from the ground state of argon ion, because of good matching in the excitation energy as well as the conservation of the total spin before and after the collision. An enhancement factor of the emission intensity for various Fe II lines could be obtained from a deviation from the normal Boltzmann plot, which comprised the emission lines of 4.7-5.8 eV. It would roughly correspond to a contribution of the charge transfer excitation to the excited levels of iron ion, suggesting that the charge-transfer collision could elevate the number density of the corresponding excited levels by a factor of ca.104. The Boltzmann plots give important information on the reason why a variety of iron ionic lines can be emitted from glow discharge plasmas.

Acid-Base Chemistry of White Wine: Analytical Characterisation and Chemical Modelling

PubMed Central

Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

2012-01-01

A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic “wine” especially adapted for testing. PMID:22566762

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.