Biomedical subjects

R Schurhammer

Publications and source records attributed to R Schurhammer.

5 recordsLinked to original sources

PubMed2006

Molecular dynamics simulations of the aqueous interface with the [BMI][PF6] ionic liquid: Comparison of different solvent models.

We report a Molecular Dynamics (MD) study of the interface between water and the hygroscopic room temperature Ionic Liquid "IL" [BMI][PF6] (1-butyl-3-methyl-imidazolium hexafluorophosphate), comparing the TIP3P, SPC/E and TIP5P models for water and two IL models where the ions are +/-1 or +/-0.9 charged. A recent MD study (A. Chaumont, R. Schurhammer and G. Wipff, J. Phys. Chem. B, 2005, 109, 18964) showed that using TIP3P water in conjunction with the IL(+/-1) model led to water-IL mixing without forming an interface, whereas a biphasic system could be obtained with the IL(+/-0.9) model. With the TIP5P and SPC/E models, the juxtaposed aqueous and IL phases are found to remain distinct for at least 20 ns. The resulting IL humidity, exaggerated with the IL(+/-1) model, is in better agreement with experiment using the IL(+/-0.9) model. We also report demixing simulations on the "randomly mixed" liquids, using the IL(+/-0.9) model for the ionic liquid. With the three tested water models, the phases separate very slowly ( approximately 20 ns or more) compared to "classical" chloroform-water mixtures (less than 1 ns), leading to biphasic systems similar to those obtained after equilibration of the juxtaposed liquids. The characteristics of the interface (size, polarity, ion orientation, electrostatic potential) are compared with the different models. Possible reasons why, among the three tested water models, the widely-used TIP3P model exaggerates the inter-solvent mixing, are analyzed. The difficulty in computationally and experimentally equilibrating water-IL mixtures is attributed to the slow dynamics and micro-heterogeneity of the IL and to the different states of water in the IL phase.

Computer Simulation↗

PubMed2006

Surfactant behavior of "ellipsoidal" dicarbollide anions: a molecular dynamics study.

We report a molecular dynamics study of cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)X(3))(2)Co](-) (XCD(-)) commonly used in liquid-liquid extraction (X = H, Me, Cl, or Br), showing that these anions, although lacking the amphiphilic topology, behave as anionic surfactants. In pure water, they display "hydrophobic attractions", leading to the formation of aggregates of different sizes and shapes depending on the counterions. When simulated at a water/"oil" interface, the different anions (HCD(-), MeCD(-), CCD(-), and BrCD(-)) are found to be surface active. As a result, the simulated M(n+) counterions (M(n+) = Na(+), K(+), Cs(+), H(3)O(+), UO(2)(2+), Eu(3+)) concentrate on the aqueous side of the interface, forming a "double layer" whose characteristics are modulated by the hydrophobic character of the anion and by M(n+). The highly hydrophilic Eu(3+) or UO(2)(2+) cations that are generally "repelled" by aqueous interfaces are attracted by dicarbollides near the interface, which is crucial as far as the mechanism of assisted cation extraction to the oil phase is concerned. These cations interact with interfacial XCD(-) in their fully hydrated Eu(H(2)O)(9)(3+) and UO(2)(H(2)O)(5)(2+) forms, whereas the less hydrophilic monocharged cations display intimate contacts via their X substituents. The results obtained with the TIP3P and OPLS models for the solvents are confirmed with other water models (TIP5P or a polarizable 4P-Pol water) and with more polar "oil" models. The importance of interfacial phenomena is further demonstrated by simulations with a high oil-water ratio, leading to the formation of a micelle covered with CCD's. We suggest that the interfacial activity of dicarbollides and related hydrophobic anions is an important feature of synergism in liquid-liquid extraction of hard cations (e.g., for nuclear waste partitioning).

Anions↗

PubMed2005

Aqueous interfaces with hydrophobic room-temperature ionic liquids: a molecular dynamics study.

We report a molecular dynamics study of the interface between water and (macroscopically) water-immiscible room-temperature ionic liquids "ILs", composed of PF6(-) anions and butyl- versus octyl-substituted methylimidazolium+ cations (noted BMI+ and OMI+). Because the parameters used to simulate the pure ILs were found to exaggerate the water/IL mixing, they have been modified by scaling down the atomic charges, leading to better agreement with the experiment. The comparison of [OMI][PF6] versus [BMI][PF6] ILs demonstrates the importance of the N-alkyl substituent on the extent of solvent mixing and on the nature of the interface. With the most hydrophobic [OMI][PF6] liquid, the "bulk" IL phase is dryer than with the [BMI][PF6] liquid. At the interface, the OMI+ cations retain direct contacts with the bulk IL, whereas the more hydrophilic PF6(-) anions gradually dilute in the local water micro-environment and are thus isolated from the "bulk" IL. The interfacial OMI+ cations are ordered with their imidazolium moiety pointing toward the aqueous side and their octyl chains toward the IL side of the interface. With the [BMI][PF6] liquid, the system gradually evolves from an IL-rich to a water-rich medium, leading to an ill-defined interfacial domain with high intersolvent mixing. As a result, the BMI+ cations are isotropically oriented "at the interface". Because the imidazolium cations are more hydrophobic than the PF6(-) anions, the charge distribution at the interface is heterogeneous, leading to a positive electrostatic potential at the interface with the two studied ILs. Mixing-demixing simulations on [BMI][PF6]/water mixtures are also reported, comparing Ewald versus reaction field treatments of electrostatics. Phase separation is very slow (at least 30 ns), in marked contrast with mixtures involving classical organic liquids, which separate in less than 0.5 ns at the microscopic level. The results allow us to better understand the specificity of the aqueous interfaces with hydrophobic ionic liquids, compared with classical organic solvents, which has important implications as far as the mechanism of liquid-liquid ion extraction is concerned.

Journal Article↗

PubMed2005

Effect of the TBP and water on the complexation of uranyl nitrate and the dissolution of nitric acid into supercritical CO2. A Theoretical Study.

We report theoretical studies on the complexation of uranyl nitrate and the dissolution of nitric acid in supercritical CO2 by TBP. According to quantum mechanical calculations, TBP (modeled by trimethyl phosphate TMP) displays stronger hydrogen-bonding interactions with HNO3 than with H2O, and this has been modeled in force-field calculations. Different combinations of water, TBP, and acid are compared in SC-CO2 and simulated by molecular dynamics (MD), demonstrating the importance of TBP and water concentrations. In MD simulations, which started from "random" mixtures of water, TBP, nitric acid, and uranyl nitrate, complexation of uranyl by TBP is observed and the yield increases with the TBP concentration. TBP molecules are also necessary to dissolve nitric acid in the supercritical phase. Indeed, without TBP, nitric acid alone self aggregates via hydrogen-bonding interactions. Adding water to this solution leads to the formation of water microdomains containing the acid and uranyl salts. The simulations show that a high TBP/nitric acid ratio is needed to fully dissolve the acid in the supercritical phase and to form CO2-philic UO2(NO3)2(TBP)2 complexes. The resulting hydrogen-bonding and solvation patterns are analyzed. The results are consistent with experimental observations and provide microscopic views of this important extraction system.

Journal Article↗

PubMed2000

Halide anion recognition in water by a hexaprotonated octaaza-cryptand: a molecular dynamics investigation.

Based on molecular dynamics simulations, we describe the F- versus Cl- complexation by an hexaprotonated cryptand L6+ in aqueous solution, in order to elucidate their structures, solvation properties and the status of external halide counterions. In water, F- and Cl- simulated inclusive complexes adopt a structure somewhat different from the solid state structure of the F- complex: The anion binding involves two diammonium bridges only, and the accompanying counterions are dissociated from the +5 charged complex. A remarkable result is obtained for the dissociated L6+,3F- ,3Cl- system, where spontaneous complexation of F- (the anion which forms the most stable complex with L6+) takes place during the dynamics. The resulting complex is of facial type; this suggests that the equilibrium involves multiple binding modes and structures in aqueous solution. The question of F-/Cl- binding selectivity is investigated by free energy perturbations simulations which nicely reproduce the spectacular preference for F- over Cl-. Two different methodologies used for the treatment of electrostatics (standard versus Ewald calculations) yield similar conclusions.

Journal Article↗