Browse
Submit Data
Databases
API
Help

Dataset Information

39 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

ABSTRACT: At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents.

SUBMITTER: de Eulate EA

PROVIDER: S-EPMC4678505 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

de Eulate Eva Alvarez EA Silvester Debbie S DS Arrigan Damien W M DW

Angewandte Chemie (International ed. in English) 20151022 49

At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent ...[more]

PMID: 26489692

Similar Datasets

Water-assisted proton transfer in ferredoxin I.

Project description:The role of water molecules in assisting proton transfer (PT) is investigated for the proton-pumping protein ferredoxin I (FdI) from Azotobacter vinelandii. It was shown previously that individual water molecules can stabilize between Asp(15) and the buried [3Fe-4S](0) cluster and thus can potentially act as a proton relay in transferring H(+) from the protein to the μ(2) sulfur atom. Here, we generalize molecular mechanics with proton transfer to studying proton transfer reactions in the condensed phase. Both umbrella sampling simulations and electronic structure calculations suggest that the PT Asp(15)-COOH + H(2)O + [3Fe-4S](0) → Asp(15)-COO(-) + H(2)O + [3Fe-4S](0) H(+) is concerted, and no stable intermediate hydronium ion (H(3)O(+)) is expected. The free energy difference of 11.7 kcal/mol for the forward reaction is in good agreement with the experimental value (13.3 kcal/mol). For the reverse reaction (Asp(15)-COO(-) + H(2)O + [3Fe-4S](0)H(+) → Asp(15)-COOH + H(2)O + [3Fe-4S](0)), a larger barrier than for the forward reaction is correctly predicted, but it is quantitatively overestimated (23.1 kcal/mol from simulations versus 14.1 from experiment). Possible reasons for this discrepancy are discussed. Compared with the water-assisted process (ΔE ≈ 10 kcal/mol), water-unassisted proton transfer yields a considerably higher barrier of ΔE ≈ 35 kcal/mol.

| S-EPMC3129148 | biostudies-literature

Control of Selective Ion Transfer across Liquid-Liquid Interfaces: A Rectifying Heterojunction Based on Immiscible Electrolytes.

Project description:The current rectification displayed by solid-state p-n semiconductor diodes relies on the abundance of electrons and holes near the interface between the p-n junction. In analogy to this electronic device, we propose here the construction of a purely ionic liquid-state electric rectifying heterojunction displaying an excess of monovalent cations and anions near the interface between two immiscible solvents with different dielectric properties. This system does not need any physical membrane or material barrier to show preferential ion transfer but relies on the ionic solvation energy between the two immiscible solvents. We construct a simple device, based on an oil/water interface, displaying an asymmetric behavior of the electric current as a function of the polarity of an applied electric field. This device also exhibits a region of negative differential conductivity, analogous to that observed in brain and heart cells via voltage clamp techniques. Computer simulations and mean field theory calculations for a model of this system show that the application of an external electric field is able to control the bulk concentrations of the ionic species in the immiscible liquids in a manner that is asymmetric with respect to the polarity or direction of the applied electric field. These properties make possible to enhance or suppress selective ion transport at liquid-liquid interfaces with the application of an external electric field or electrostatic potential, mimicking the function of biological ion channels, thus creating opportunities for varied applications.

| S-EPMC5126720 | biostudies-literature

Water in Protic Ionic Liquid Electrolytes: From Solvent Separated Ion Pairs to Water Clusters.

Project description:The large electrochemical and cycling stability of "water-in-salt" systems have rendered promising prospective electrolytes for batteries. The impact of addition of water on the properties of ionic liquids has already been addressed in several publications. In this contribution, we focus on the changes in the state of water. Therefore, we investigated the protic ionic liquid N-butyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide with varying water content at different temperatures with the aid of molecular dynamics simulations. It is revealed that at very low concentrations, the water is well dispersed and best characterized as shared solvent molecules. At higher concentrations, the water forms larger aggregates and is increasingly approaching a bulk-like state. While the librational and rotational dynamics of the water molecules become faster with increasing concentration, the translational dynamics are found to become slower. Further, all dynamics are found to be faster if the temperature increases. The trends of these findings are well in line with the experimental measured conductivities.

| S-EPMC8456901 | biostudies-literature

Water at hydrophobic interfaces delays proton surface-to-bulk transfer and provides a pathway for lateral proton diffusion.

Project description:Fast lateral proton migration along membranes is of vital importance for cellular energy homeostasis and various proton-coupled transport processes. It can only occur if attractive forces keep the proton at the interface. How to reconcile this high affinity to the membrane surface with high proton mobility is unclear. Here, we tested whether a minimalistic model interface between an apolar hydrophobic phase (n-decane) and an aqueous phase mimics the biological pathway for lateral proton migration. The observed diffusion span, on the order of tens of micrometers, and the high proton mobility were both similar to the values previously reported for lipid bilayers. Extensive ab initio simulations on the same water/n-decane interface reproduced the experimentally derived free energy barrier for the excess proton. The free energy profile G(H(+)) adopts the shape of a well at the interface, having a width of two water molecules and a depth of 6 ± 2RT. The hydroniums in direct contact with n-decane have a reduced mobility. However, the hydroniums in the second layer of water molecules are mobile. Their in silico diffusion coefficient matches that derived from our in vitro experiments, (5.7 ± 0.7) 10(-5) cm(2) s(-1). Conceivably, these are the protons that allow for fast diffusion along biological membranes.

| S-EPMC3382531 | biostudies-literature

Anions dramatically enhance proton transfer through aqueous interfaces.

Project description:Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HNO(3) does not dissociate upon collision with the surface of water unless a few ions (> 1 per 10(6) H(2)O) are present. By applying online electrospray ionization mass spectrometry to monitor in situ the surface of aqueous jets exposed to HNO(3(g)) beams we found that NO(3)(-) production increases dramatically on > 30-?M inert electrolyte solutions. We also performed quantum mechanical calculations confirming that the sizable barrier hindering HNO(3) dissociation on the surface of small water clusters is drastically lowered in the presence of anions. Anions electrostatically assist in drawing the proton away from NO(3)(-) lingering outside the cluster, whose incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water-hydrophobe boundaries and its remarkable sensitivity to electrostatic effects.

| S-EPMC3387034 | biostudies-literature

One-dimensional <i>vs.</i> two-dimensional proton transport processes at solid-liquid zinc-oxide-water interfaces.

Project description:Long-range charge transport is important for many applications like batteries, fuel cells, sensors, and catalysis. Obtaining microscopic insights into the atomistic mechanism is challenging, in particular if the underlying processes involve protons as the charge carriers. Here, large-scale reactive molecular dynamics simulations employing an efficient density-functional-theory-based neural network potential are used to unravel long-range proton transport mechanisms at solid-liquid interfaces, using the zinc oxide-water interface as a prototypical case. We find that the two most frequently occurring ZnO surface facets, (101[combining macron]0) and (112[combining macron]0), that typically dominate the morphologies of zinc oxide nanowires and nanoparticles, show markedly different proton conduction behaviors along the surface with respect to the number of possible proton transfer mechanisms, the role of the solvent for long-range proton migration, as well as the proton transport dimensionality. Understanding such surface-facet-specific mechanisms is crucial for an informed bottom-up approach for the functionalization and application of advanced oxide materials.

| S-EPMC6349017 | biostudies-literature

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries.

Project description:Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

| S-EPMC4148675 | biostudies-literature

Origin of proton affinity to membrane/water interfaces.

Project description:Proton diffusion along biological membranes is vitally important for cellular energetics. Here we extended previous time-resolved fluorescence measurements to study the time and temperature dependence of surface proton transport. We determined the Gibbs activation energy barrier ?G ‡r that opposes proton surface-to-bulk release from Arrhenius plots of (i) protons' surface diffusion constant and (ii) the rate coefficient for proton surface-to-bulk release. The large size of ?G ‡r disproves that quasi-equilibrium exists in our experiments between protons in the near-membrane layers and in the aqueous bulk. Instead, non-equilibrium kinetics describes the proton travel between the site of its photo-release and its arrival at a distant membrane patch at different temperatures. ?G ‡r contains only a minor enthalpic contribution that roughly corresponds to the breakage of a single hydrogen bond. Thus, our experiments reveal an entropic trap that ensures channeling of highly mobile protons along the membrane interface in the absence of potent acceptors.

| S-EPMC5495794 | biostudies-literature

Mechanistic Studies on Rhodium-Catalyzed Chemoselective Cycloaddition of Ene-Vinylidenecyclopropanes: Water-Assisted Proton Transfer.

Project description:Rhodium-catalyzed cycloaddition reactions are a powerful tool for the construction of polycyclic compounds. Combined experimental and DFT studies were used to investigate the temperature-controlled chemoselectivity of cationic rhodium-catalyzed intramolecular cycloaddition reactions of ene-vinylidenecyclopropanes. After a series of mechanistic studies, it was found that trace amounts of water in the reaction system play an important role in generating the product with endo double bond located on a five-membered ring and revealed that trace amounts of water in the reaction system, including the rhodium catalyst, substrate and solvent, were sufficient to promote the formation of the product with endo double bond located on a five-membered ring, and additional water could not further accelerate the reaction. DFT calculation results show that the addition of water indeed significantly lowers the energy barrier of the proton transfer step, making the formation of the product with endo double bond located on a five-membered ring more likely to occur and confirming the rationality of water-assisted proton transfer occurring in the selective access to the product with endo double bond located on a five-membered ring.

| S-EPMC10934677 | biostudies-literature

Photo-Triggered Reversible Phase Transfer of Azobenzene-Based Ionic Liquid Surfactants between Oil and Water.

Project description:The reversible phase transfer of compounds between two immiscible liquid phases has many applications in a wide range of fields, and ionic liquids have been widely used as potential functional solvents and catalysts. However, photo-triggered reversible phase transfer of ionic liquids between the organic phase and water phase has not been reported so far. In the present work, the reversible phase transfer of six kinds of azobenzene-based ionic liquid surfactants between the organic phase and water phase is investigated by alternative irradiation of UV and visible light. Factors affecting the transfer efficiency, such as chemical structure and concentration of the ionic liquid surfactants, equilibrium photo-isomerization degree, and the aggregation state of ionic liquid surfactants are investigated in detail. It is shown that transfer efficiency greater than 89% was achieved under optimal conditions, equilibrium photo-isomerization degree of the ionic liquid surfactants is the main factor to determine their transfer efficiencies, and the aggregation of cis-isomers is not beneficial for the transfer.

| S-EPMC6479859 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data