Synthesis and properties of thiazoline based ionic liquids derived from the chiral pool

A novel class of chiral ionic liquids derived from amino alcohols is prepared in multi-gram scale. Their potential in chiral recognition is shown in a preliminary example with racemic Mosher's acid salt.     

The origin of the electrode effect in various electrolytes

The problem of the origin of electrode effects in various electrolytes is studied on the ground of Fourier's equation. Thus the electrolysis time elapsed before the occurrence of an electrode effect is shown to be equal to the calculated time which is the time necessary to bring the temperature of the electrolyte surrounding the electrode up to its boiling point. Then we can conclude in all cases investigated that the electrode effects are induced by a Joule effect heating of the electrolyte.     

Ab-initio study of localization of an excess electron in sodium halide clusters

The equilibrium geometries of Na _n F _n and Na _n F _n?1 are optimized forn=2, 3, 4 at the SCF level. The Na _n F _n molecules appear as formed by Na⁺ and F^? ions. The paper studies the localization of the excess electron in the Na _n F _n?1 molecules. Na _n F _n?1 is obtained by removing from Na _n F _n a fluorine atom, and the excess electron takes the place of this lacking center, and allows a weak bond between the neighbouring Na atoms. Secondary minimum geometries, for which the excess electron has no defined place, are also studied.     

Adsorption of lysozyme on a hemodialysis sulfonated polyacrylonitrile membrane, with and without preadsorbed poly(ethyleneimine) on the external faces

We present the influence of pH, from pH 4 to 10, with a focus on the neutral range, on the adsorption of lysozyme (isoelectric point pI=11) on a sulphonated membrane and the same membrane pre-treated with poly(ethyleneimine) (PEI). We found a steep increase of the adsorbed amount above pH 6 in phosphate buffer. The adsorbed amount was about twice as low in Tris buffer, around the neutral pH. The difference between the two types of buffer is attributed to their different ionic composition. High interfacial concentration in phosphate buffer is especially linked to the phosphate divalent anions. In the presence of divalent sulphate anions, we measured the same level of interfacial concentration than with phosphate buffer. With the PEI pre-treated membrane, we observed, on the time scale of our experiments (15–20 h), similar adsorbed amounts than on the raw membrane, showing that the PEI layer does not constitute a true barrier to the penetration of lysozyme into the membrane core. However, its presence leads to a slower adsorption rate in a system where convection does not occur through the membrane.     

Advances in Characterisation Methods for Sol-Gel Derived Materials: High Resolution Solid State Nuclear Magnetic Resonance

The objective of this paper is to discuss the recent advances in high resolution solid state Nuclear Magnetic Resonance (NMR) to characterise sol-gel derived materials. The first part will be focused on methods to describe M _i --O--M _j connectivities in sol-gel networks. After a brief review on techniques based on scalar J-coupling, we will focus on the use of ¹⁷O solid state NMR experiments. Then in a second part, techniques to probe through-space interactions in hybrid networks will be described, with a particular emphasis on the use of high resolution ¹H solid state NMR sequences and related two-dimensional homonuclear or heteronuclear correlations.     

Synthesis and characterization of a novel cyclic aluminophosphinate: structure and solid-state NMR study

We present the structure and a multinuclear solid-state NMR study of a new cyclic aluminophosphinate. The crystallographic structure of [Al(2)(HC(6)H(5)PO(2))(2)(C(4)H(9)OH)(8)]Cl(4) (compound 1) was obtained at low temperature (a = 11.830(7) A, b = 14.216(6) A, c = 17.790(6) A, beta = 91.25(4) degrees, monoclinic, P21/c, Z = 2). (13)C IRCP (inversion recovery cross polarization) and NQS (non quaternary suppression) NMR experiments allowed the complete assignment of the quaternary carbon atom of the phenyl ring and the precise determination of the isotropic /(1)J(P-C)/ coupling constant. (31)P CP MAS dynamics was carefully studied by varying the contact time. Dipolar oscillations even at slow MAS were observed. Up to 11 kHz, these oscillations were more pronounced, and the P-H distance was easily extracted. (27)Al NMR quadrupolar parameters for 1 were obtained with very good accuracy, and unusual satellite transition splitting was observed. Furthermore, the isotropic lines of the inner and outer transitions were clearly observable, leading to the unambiguous determination of the quadrupolar parameters.     

A new crystalline phase of nitric acid dihydrate

The crystal structure of a new high-temperature phase of nitric acid dihydrate, HNO₃·2H₂O, has been determined at 225 K by single-crystal X-ray diffraction. The H atom of the nitric acid is delocalized to one water mol­ecule, leading to an association of equimolar NO₃⁻ and H₅O₂⁺ ionic groups. The asymmetric unit contains two mol­ecules of HNO₃·2H₂O. The two independent mol­ecules are related by a pseudo-twofold c axis, by a translation of 0.54 (approximately ½) along b , with a mean atomic distance difference of 0.3 Å, except for one H atom of the water mol­ecules (1.5 Å), because of their different orientations in the two mol­ecules. The two independent mol­ecules, linked by strong hydrogen bonds, are arranged in layers. These layers are linked by weaker hydrogen bonds oriented approximately along the c axis. A three-dimensional hydrogen-bond network is observed.     

Influence of Electrolyte on the Electrode/Electrolyte Interface Formation on InSb Electrode in Mg-Ion Batteries

Achieving the full potential of magnesium-ion batteries (MIBs) is still a challenge due to the lack of adequate electrodes or electrolytes. Grignard-based electrolytes show excellent Mg plating/stripping, but their incompatibility with oxide cathodes restricts their use. Conventional electrolytes like bis(trifluoromethanesulfonyl)imide ((Mg(TFSI)₂) solutions are incompatible with Mg metal, which hinders their application in high-energy Mg batteries. In this regard, alloys can be game changers. The insertion/extraction of Mg²⁺ in alloys is possible in conventional electrolytes, suggesting the absence of a passivation layer or the formation of a conductive surface layer. Yet, the role and influence of this layer on the alloys performance have been studied only scarcely. To evaluate the reactivity of alloys, we studied InSb as a model material. Ex situ X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy were used to investigate the surface behavior of InSb in both Grignard and conventional Mg(TFSI)₂/DME electrolytes. For the Grignard electrolyte, we discovered an intrinsic instability of both solvent and salt against InSb. XPS showed the formation of a thick surface layer consisting of hydrocarbon species and degradation products from the solvent (THF) and salt (C₂H₅MgCl−(C₂H₅)₂AlCl). On the contrary, this study highlighted the stability of InSb in Mg(TFSI)₂ electrolyte.     

On the performance of various adaptive preconditioned GMRES strategies

This paper compares the performance on linear systems of equations of three similar adaptive accelerating strategies for restarted GMRES. The underlying idea is to adaptively use spectral information gathered from the Arnoldi process. The first strategy retains approximations to some eigenvectors from the previous restart and adds them to the Krylov subspace. The second strategy also uses approximated eigenvectors to define a preconditioner at each restart. This paper designs a third new strategy which combines elements of both previous approaches. Numerical results show that this new method is both more efficient and more robust. © 1998 John Wiley & Sons, Ltd.