Induced Protic Behaviour in Aprotonic Ionic Liquids by Anion Basicity for Efficient Carbon Dioxide Capture

The interactions between aprotonic tetrabutylphosphonium carboxylate ionic liquids (ILs), [P_{4 4 4 4}][C_nCOO] (n=1, 2 and 7), and water were investigated. The cation-anion interactions occur via the α-¹H on [P_{4 4 4 4}]⁺ and the carboxylate headgroup of the anion. Upon addition, H₂O localises around the carboxylate headgroups, inducing an electron inductive effect towards the oxygens, leading to ion-pair separation. Studies with D₂O and [P_{4 4 4 4}][C_nCOO] revealed protic behaviour of the systems, with proton/deuterium exchange occurring at the α-¹H of the cation, promoted by the basicity of the anion, forming an intermediate ylide. The greater influence of van der Waals forces of the [P_{4 4 4 4}][C₇COO] system allows for re-orientation of the ions through larger interdigitation. The protic behaviour of the neat ILs allows for CO₂ to be chemically absorbed on the ylide intermediate, forming a phosphonium-carboxylate zwitterion, signifying proton exchange occurs even in the absence of H₂O. The absorption of CO₂ in equimolar IL-H₂O mixtures forms a hydrogen carbonate, through a proposed reaction of the CO₂ with an intermediate hydroxide, and carboxylic acid.     

New variants of bundle methods

In this paper we describe a number of new variants of bundle methods for nonsmooth unconstrained and constrained convex optimization, convex—concave games and variational inequalities. We outline the ideas underlying these methods and present rate-of-convergence estimates.Corresponding author.     

How do azoles inhibit cytochrome P450 enzymes? A density functional study

To examine how azole inhibitors interact with the heme active site of the cytochrome P450 enzymes, we have performed a series of density functional theory studies on azole binding. These are the first density functional studies on azole interactions with a heme center and give fundamental insight into how azoles inhibit the catalytic function of P450 enzymes. Since azoles come in many varieties, we tested three typical azole motifs representing a broad range of azole and azole-type inhibitors: methylimidazolate, methyltriazolate, and pyridine. These structural motifs represent typical azoles, such as econazole, fluconazole, and metyrapone. The calculations show that azole binding is a stepwise mechanism whereby first the water molecule from the resting state of P450 is released from the sixth binding site of the heme to create a pentacoordinated active site followed by coordination of the azole nitrogen to the heme iron. This process leads to the breaking of a hydrogen bond between the resting state water molecule and the approaching inhibitor molecule. Although, formally, the water molecule is released in the first step of the reaction mechanism and a pentacoordinated heme is created, this does not lead to an observed spin state crossing. Thus, we show that release of a water molecule from the resting state of P450 enzymes to create a pentacoordinated heme will lead to a doublet to quartet spin state crossing at an Fe-OH(2) distance of approximately 3.0 A, while the azole substitution process takes place at shorter distances. Azoles bind heme with significantly stronger binding energies than a water molecule, so that these inhibitors block the catalytic cycle of the enzyme and prevent oxygen binding and the catalysis of substrate oxidation. Perturbations within the active site (e.g., a polarized environment) have little effect on the relative energies of azole binding. Studies with an extra hydrogen-bonded ethanol molecule in the model, mimicking the active site of the CYP121 P450, show that the resting state and azole binding structures are close in energy, which may lead to chemical equilibrium between the two structures, as indeed observed with recent protein structural studies that have demonstrated two distinct azole binding mechanisms to P450 heme.     

Error bounds,metric subregularity and stability in Generalized Nash Equilibrium Problems with nonsmooth payoff functions

In this paper, we study the calmness of a generalized Nash equilibrium problem (GNEP) with non-differentiable data. The approach consists in obtaining some error bound property for the KKT system associated with the generalized Nash equilibrium problem, and returning to the primal problem thanks to the Slater constraint qualification.     

Antibody capture by mixed-mode chromatography: a comprehensive study from determination of optimal purification conditions to identification of contaminating host cell proteins

We evaluated mixed mode chromatography for the capture of recombinant antibodies from CHO cell culture supernatants. We studied PPA HyperCel, HEA HyperCel, MEP HyperCel and Capto adhere resins, which all contain hydrophobic and cationic groups. A microplate approach combined with DoE modeling allowed the exploration of the complex behaviors of these mixed mode resins. Optimal conditions for antibody purification and host cell proteins (HCPs) elimination were determined and then directly up-scaled to laboratory columns. Then we used mass spectrometry to identify the major HCPs potentially coeluted with the antibody. Differences between the four resins in terms of amount, complexity and identity of the HCPs present in the elution fractions were investigated.     

Focusing of alkali earth metals in ligand step gradient

A capillary electroseparation technique for focusing and selective pre-concentration of metal chelates with subsequent on-line isotachophoresis (ITP) analysis was developed and verified. The ions of alkali earth metals (Mg, Ca, Sr, and Ba) were pre-concentrated from the mixture and analyzed. The focusing of the metals was carried out in a ligand step gradient, which was created by the addition of a convenient ligand agent to the regular stationary pH step gradient. The analytical procedure consisted of three steps. During the first step, the metal ions were electrokinetically continuously dosed into the column where they were selectively trapped on the stationary ligand step gradient in the form of unmoving zones of chelate complexes with effectively zero charge. After a detectable amount of analyte was accumulated, the dosing was stopped. The accumulated zones were mobilized to the analytical column, where they were analyzed by the ITP method with conductivity or photometric detection. The proper electrolyte systems for dosing, mobilizing, and analyzing in isoelectric focusing (IEF), moving boundary electrophoresis (MBE), and ITP modes were consequently developed and put into practice. The trapping selectivity can be regulated by the choice of pH and convenient complexing agents. A mixture of alkali earth metals were used as model analytes. Using a 3000 s dosing time, the proposed method improved the detection limit by 5-29 times in comparison to analysis by ITP with classical injection.     

Ultrasonic characterization of a fluid layer using a broadband transducer

A measurement method is proposed for the ultrasonic characterization of a fluid layer, corresponding to the resin transfer molding (RTM) manufacturing process. The ultrasonic velocity and attenuation of the silicone oil are measured in three samples having different viscosities. The measurement method is established on the basis of the attenuation of ultrasonic waves in fluids. A correction of the beam diffraction is implemented to improve measurement precision. A single element transducer with central frequency of 15 MHz is used. The tested fluids simulate the industrial resin used to manufacture composite materials. When injecting this resin, its viscosity increases until it reaches a critical state of polymerization. In this paper we focus on ultrasonic characterization of three fluids representing three intermediate cases of fluid resin during its injection before reaching the polymerization state.     

Thermodynamics of a Bose-Einstein condensate with free magnetization

We study thermodynamic properties of a gas of spin 3(52)Cr atoms across Bose-Einstein condensation. Magnetization is free, due to dipole-dipole interactions. We show that the critical temperature for condensation is lowered at extremely low magnetic fields, when the spin degree of freedom is thermally activated. The depolarized gas condenses in only one spin component, unless the magnetic field is set below a critical value, below which a nonferromagnetic phase is favored. Finally, we present a spin thermometry efficient even below the degeneracy temperature.