High pressure CO2 absorption studies on imidazolium-based ionic liquids:Experimental and simulation approaches

A combined experimental-computational study on the CO absorption on 1-butyl-3-methylimidazolium hexafluophosphate, 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide, and 1-butyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide ionic liquids is reported. The reported results allowed to infer a detailed nanoscopic vision of the absorption phenomena as a function of pressure and temperature. Absorption isotherms were measured at 318 and 338K for pressures up to 20MPa for ultrapure samples using a state-of-the-art magnetic suspension densimeter, for which measurement procedures are developed. A remarkable swelling effect upon CO absorption was observed for pressures higher than 10MPa, which was corrected using a method based on experimental volumetric data. The experimental data reported in this work are in good agreement with available literature isotherms. Soave-Redlich-Kwong and Peng-Robinson equations of state coupled with bi-parametric van der Waals mixing rule were used for successful correlations of experimental high pressure absorption data. Molecular dynamics results allowed to infer structural, energetic and dynamic properties of the studied CO+ionic liquids mixed fluids, showing the relevant role of the strength of anion-cation interactions on fluid volumetric properties and CO absorption. © 2012 Elsevier B.V.

Halometallate ionic liquids – revisited

Ionic liquids with chlorometallate anions may not have been the first ionic liquids, however, it was their development that lead to the recognition that ionic liquids are a distinct, and useful, class of (functional) materials. While much of the phenomenal interest and attention over the past two decades has focussed on ‘air and water stable’ ionic liquids, research and application of chlorometallate systems has continued unabated albeit largely out of the main spotlight. The defining characteristic of chlorometallates is the presence of complex anionic equilibria, which depend both on the type and on the concentration of metal present, and leads directly to their characteristic and individual properties. Here, we review the experimental techniques that can be applied to study and characterise the anion speciation in these ionic liquids and, using recent examples, illustrate how their applications base is evolving beyond traditional applications in Lewis acidic catalysis and electrochemistry through to uses as soft and component materials, in the ionothermal synthesis of semiconductors, gas storage systems and key components in the development of biomass processing.

Novel chiral ionic liquids:physicochemical properties and investigation of the internal rotameric behaviour in the neat system

Optically active S-alkyl-N, N'-bis((S)-1-phenylethyl) thiouronium salts, abbreviated as (S)-[Cnpetu] Y (where Y is an anion; n = 1, 2, 3, 4, 6, 8, 10, 12 or 16), have been prepared and studied by a broad spectrum of analyses. This consists of density, viscosity, and conductivity determination, followed by a discussion of relevant correlations. Unusual trends depending on the S-alkyl chain length were documented for (S)-[Cnpetu][ NTf2] series (where [NTf2] = bis{(trifluoromethyl) sulfonyl} amide), including the viscosity decreasing with increasing chain length, and the conductivity showing a maximum between the S-butyl and the S-hexyl derivative. In addition, a hindered rotamerism of the thiouronium cation in dmso-d(6) solution was recognised by H-1 and C-13 NMR techniques. Thorough analysis of NMR spectra confirmed that the main contribution comes from rotation about the partial double C-S bond. For the first time, a neat thiouronium ionic liquid system has been subjected to quantitative analysis of hindered rotamerism by dynamic NMR coalescence studies, with estimated activation energy for rotation of 63.9 +/- 0.4 kJ mol(-1). Finally, the application of (S)-[C(n)petu] Y salts as chiral discriminating agents for carboxylates by 1H NMR spectroscopy was further investigated, demonstrating the influence of the S-alkyl chain length on chiral recognition; (S)-[C(2)petu][NTf2] ionic liquid with the mandelate anion gave the best results.

Pressure effect on vibrational frequency and dephasing of 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids

Raman spectra in the range of the totally symmetric stretching mode of the [PF6]− anion, νs(PF6), have been measured for 1-alkyl-3-methylimidazolium ionic liquids [CnC1im][PF6], for n = 4, 6, and 8, as a function of pressure at room temperature. The ionic liquids [C6C1im][PF6] and [C8C1im][PF6] remain in an amorphous phase up to 3.5 GPa, in contrast to [C4C1im][PF6], whichcrystallizes above ∼0.5 GPa. Equations of state based either on a group contribution model or Carnahan-Starling-van der Waals model have been used to estimate the densities of the ionic liquids at high pressures. The shifts of the vibrational frequency of νs(PF6) with density observed in [C6C1im][PF6] and in [C8C1im][PF6] have been calculated by a hard-sphere model of a pseudo-diatomic solute under short-range repulsive interactions with the neighboring particles. The stochastic model of Kubo for vibrational dephasing has been used to obtain the amplitude of vibrational frequency fluctuation, ⟨Δω 2⟩, and the relaxation time of frequency fluctuation, τ c , as a function of density by Raman band shape analysis of the νs(PF6) mode of [C6C1im][PF6] and [C8C1im][PF6].

Characterization, crystallization and preliminary X—ray diffraction analysis of acutohaemolysin, a haemolytic toxin from Agkistrodon acutus venom

Acutohaemolysin, a phospholipase A2 (PLA2) from the venom of the snake Agkistrodon acutus, has been isolated and purified to homogeneity by anion-exchange chromatography on a DEAE-Sepharose column followed by cation-exchange chromatography on a CM-Sepharose column. It is an alkaline protein with an isoelectric point of 10.5 and is comprised of a single polypeptide chain of 13 938 Da. Its N-terminal amino-acid sequence shows very high similarity to Lys49-type PLA2 proteins from other snake venoms. Although its PLA2 enzymatic activity is very low, acutohaemolysin has a strong indirect haemolytic activity and anticoagulant activity. Acutohaemolysin crystals with a diffraction limit of 1.60 Å were obtained by the hanging-drop vapour-diffusion method. The crystals belong to the space group C2, with unit-cell parameters a = 45.30, b = 59.55, c = 46.13 Å, [beta] = 117.69°. The asymmetric unit contains one molecule

Molecular mechanism and physiological role of active-deactive transition of mitochondrial complex I

The unique feature ofmitochondrial complex I is the so-called A/D transition (active-deactive transition). The A-form catalyses rapid oxidation of NADH by ubiquinone (k ~10 min) and spontaneously converts into the D-form if the enzyme is idle at physiological temperatures. Such deactivation occurs in vitro in the absence of substrates or in vivo during ischaemia, when the ubiquinone pool is reduced. The D-form can undergo reactivation given both NADH and ubiquinone availability during slow (k ~1-10 min) catalytic turnover(s). We examined known conformational differences between the two forms and suggested a mechanism exerting A/D transition of the enzyme. In addition, we discuss the physiological role of maintaining the enzyme in the D-form during the ischaemic period. Accumulation of the D-form of the enzyme would prevent reverse electron transfer from ubiquinol to FMN which could lead to superoxide anion generation. Deactivation would also decrease the initial burst of respiration after oxygen reintroduction. Therefore the A/D transition could be an intrinsic protective mechanism for lessening oxidative damage during the early phase of reoxygenation. Exposure of Cys of mitochondrially encoded subunit ND3 makes the Dform susceptible for modification by reactive oxygen species and nitric oxide metabolites which arrests the reactivation of the D-form and inhibits the enzyme. The nature of thiol modification defines deactivation reversibility, the reactivation timescale, the status of mitochondrial bioenergetics and therefore the degree of recovery of the ischaemic tissues after reoxygenation.

New insights into dihydrogenphosphate recognition with dirhenium(I) tricarbonyl complexes bridged by a thiourea moiety

Three thiourea bridged 2,2’-bipyridine ligands bearing either a single thiourea group (L1), or two units separated by either a para (L2) or meta-substituted (L3) aromatic spacer, along with the corresponding bis(fac-tricarbonylrhenium(I)) complexes are reported. The three ligands all show the anticipated binding to acetate. However 1H NMR titrations reveal an unusual cooperative binding to, and selectivity for, two dihydrogenphosphate ions. The rhenium(I) complexes similarly demonstrate unusual sigmoidal titration curves, and in the case of {Re(CO)3Br}2(-L1) a surprisingly strong interaction to two anions. These were further exemplified in the emissive behaviour leading to the conclusion that there is an unusual interaction with dihydrogenphosphate, giving an initial increase in the emission, followed by a decrease and a blue shift in wavelength possibly as a result of partial deprotonation. It appears that dihydrogenphosphate binds cooperatively, with the addition of a second anion enhancing the interaction of the first, probably by proton transfer; this could explain the remarkable selectivity for phosphate seen with many reported anion receptors.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

Ionothermal, microwave-assisted synthesis of indium(III) selenide

Microcrystalline indium(III) selenide was prepared from a diphenyl diselenide precursor and a range of chloroindate(III) ionic liquids via a microwave-assisted ionothermal route; this is the first report on the use of either microwave irradiation or ionic liquids to prepare this material. The influence of the reaction temperature, dilution with a spectator ionic liquid and variation of the cation and the anion of the ionic liquid on the product morphology and composition were investigated. This resulted in a time-efficient and facile one-pot reaction to produce microcrystalline indium(III) selenide. The product formation in the ionic liquids has been monitored using Raman spectroscopy. The products have been characterised using PXRD, SEM and EDX. Advantages of this new route, such as the ease of solubilisation of all reactants into one phase at high concentration, the negligible vapour pressure irrespective of the reaction temperature, very fast reaction times, ease of potential scale-up and reproducibility are discussed.

Bis(tetraethylammonium) decachloro-tetramercurate(II), (Et4N)(2)[Hg4Cl10]

The structure of (Et4N)(2)[Hg4Cl10] contains dinuclear [Hg2Cl6](2-) anions and HgCl2 molecules, with definite interactions so that the anion can also be formulated as [Hg4Cl10](2-). Alternatively the compound can be written as (Et4N)(2)[Hg2Cl6][HgCl2](2). Charge balance is achieved by ordered [Et4N](+) cations. An inversion centre is situated at the centre of the [Hg2Cl6](2-) anions.

The electrochemical reduction of 1-bromo-4-nitrobenzene at zinc electrodes in a room-temperature ionic liquid: a facile route for the formation of arylzinc compounds

The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC₆H₄NO₂) at zinc microelectrodes in the [C(₄)mPyrr][NTf₂] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC₆H₄NO₂ is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.

Impaired activities of antioxidant enzymes elicit endothelial dysfunction in spontaneous hypertensive rats despite enhanced vascular nitric oxide generation

Objective: Enhanced oxidative stress is involved in mediating the endothelial dysfunction associated with hypertension. The aim of this study was to investigate the relative contributions of pro-oxidant and anti-oxidant enzymes to the pathogenesis of endothelial dysfunction in genetic hypertension. Methods: Dilator responses to endothelium-dependent and endothelium-independent agents such as acetylcholine (ACh) and sodium nitroprusside were measured in the thoracic aortas of 28-week-old spontaneously hypertensive rats (SHR) and their matched normotensive counterparts, Wistar Kyoto rats (WKY). The activity and expression (mRNA and protein levels) of endothelial nitric oxide synthase (eNOS), p22-phox, a membrane-bound component of NAD(P)H oxidase, and antioxidant enzymes, namely, superoxide dismutases (CuZn- and Mn-SOD), catalase and glutathione peroxidase (GPx), were also investigated in aortic rings. Results: Relaxant responses to ACh were attenuated in phenylephrine-precontracted SHR aortic rings, despite a 2-fold increase in eNOS expression and activity. Although the activity and/or expression of SODs, NAD(P)H oxidase (p22-phox) and GPx were elevated in SHR aorta, catalase activity and expression remained unchanged compared to WKY. Pretreatment of SHR aortic rings with the inhibitor of xanthine oxidase, allopurinol, and the inhibitor of cyclooxygenase, indomethacin, significantly potentiated ACh-induced relaxation. Pretreatment of SHR rings with catalase and Tiron, a superoxide anion (O) scavenger, increased the relaxant responses to the levels observed in WKY rings whereas pyrogallol, a O -generator, abolished relaxant responses to ACh. Conclusion: These data demonstrate that dysregulation of several enzymes, resulting in oxidative stress, contributes to the pathogenesis of endothelial dysfunction in SHR and indicate that the antioxidant enzyme catalase is of particular importance in the reversal of this defect. © 2003 European Society of Cardiology. Published by Elsevier B.V. All rights reserved.

Dendritic receptors designed to bind polyanions in both organic and aqueous media

This paper reports the synthesis of dendrons containing a spermine unit at their focal point. The dendritic branching is based on L-lysine building blocks, and has terminal oligo(ethyleneglycol) units on the surface. As a consequence of the solubilising surface groups, these dendrons have high solubility in solvents with widely different polarities (e.g., dichloromethane and water). The protonated spermine unit at the focal point is an effective anion binding fragment and, as such, these dendrons are able to bind to polyanions. This paper demonstrates that polyanions can be bound in both dichloromethane (using a dye solubilisation assay) and in water (competitive ATP binding assay). In organic media the dendritic branching appears to have a pro-active effect on the solubilisation of the dye, with more dye being solubilised by higher generations of dendron. On the other hand, in water the degree of branching has no impact on the anion binding process. We propose that in this case, the spermine unit is effectively solvated by the bulk solvent and the dendritic branching does not need to play an active role in assisting solubility. Dendritic effects on anion binding have therefore been elucidated in different solvents. The dendritic branching plays a pro-active role in providing the anion binding unit with good solubility in apolar solvent media.

The solution structure of 1:2 phenol/N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide liquid mixtures

Neutron diffraction has been used to investigate the liquid structure of a 1:2 solution of phenol in the ionic liquid N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide at 60 ◦C, using the empirical potential structure refinement (EPSR) process to model the data obtained from the SANDALS diffractometer at ISIS. Addition of phenol results in suppression of the melting point of the pyridinium salt and formation of a room temperature solution with aromatic phenol–cation and phenol-OH to anion hydrogen-bonding interactions.