The crystal structure of the inorganic surface films formed on Mg and Li intercalation compounds and the electrode performance

A crystallographic approach was applied to elucidate the influence of the nature of the surface films on the electrochemical behavior of Li and Mg intercalation compounds. This paper presents two examples: (1) protection of graphite electrodes by Li₂CO₃ surface films, and (2) the unique electrochemical behavior of Mg-containing Chevrel phases (MgCP) obtained by different synthetic routes. In the former case, the elucidation of the protection mechanism and the explanation of the high performance of such protected electrodes are based on the analysis of possible Li-ion motion in the carbonate crystal structure. In the latter case, a combination of synthesis, electrochemistry and XRD analysis was used to explain an unusual phenomenon: the difference between the excellent electrochemical behavior of the Chevrel phase (CP) based on Cu-leached Cu₂Mo₆S₈ (CuCP), and the poor electrochemical activity of the high-temperature synthesized MgCP, with the same phase composition. It is shown that this phenomenon is caused by MgO formation on the surface of the latter material. The different surface chemistry of the MgCPs obtained by the two different synthetic routes was substantiated by revealing the correlation between the electrochemical activity and the chemical stability of these materials under ambient atmosphere conditions. Dedicated to Prof. Mikhail A. Vorotyntsev on the occasion of his 60th birthday.     

The Worpitzky identity for the groups of signed and even-signed permutations

Journal of Algebraic Combinatorics - The well-known Worpitzky identity $$\begin{aligned} (x+1)^n = \sum \limits _{k=0}^{n-1} A_{n,k} {{x+n-k} \atopwithdelims (){n}} \end{aligned}$$ provides a...     

Surface layering in ionic liquids: an X-ray reflectivity study

The surface structure and thermodynamics of two ionic liquids, based on the 1-alkyl-3-methylimidazolium cations, were studied by X-ray reflectivity and surface tensiometry. A molecular layer of a density approximately 18% higher than that of the bulk is found to form at the free surface of these liquids. In common with surface layering in liquid metals and surface freezing in melts of organic chain molecules, this effect is induced by the lower dimensionality of the surface. The concentrations of the oppositely charged ions within the surface layer are determined by chemical substitution of the anion. The temperature-dependent surface tension measurements reveal a normal, negative-slope temperature dependence. The different possible molecular arrangements within the enhanced-density surface layer are discussed.     

Organically modified sols as pseudostationary phases for microchip electrophoresis

We demonstrate that the selectivity of microchip electrophoresis separations is greatly improved by the presence of organically modified silica (Ormosil) sols in the run buffer. A negatively-charged N-(trimethoxysilylpropyl)ethylenediamine triacetic-acid (TETT)-based sol is used for improving the selectivity between nitroaromatic explosives and a methyltrimethoxysilane (MTMOS)-based sol is employed for enhancing the microchip separation of environmental pollutants, aminophenols. These sols are added to the run buffer and act as pseudostationary phases. Their presence in the run buffer changes the apparent mobility of studied solutes, and leads to a higher resolution. The observed mobilities changes reflect the interactions between the Ormosil sols and the solutes. Relevant experimental variables have been characterized and optimized. The diverse chemistry of Ormosil sols should be extremely useful for tailoring the selectivity of a wide range of electrophoresis microchip separations.     

Using spin dynamics of covalently linked radical ion pairs to probe the impact of structural and energetic changes on charge recombination

We have synthesized a series of structurally related, covalently linked electron donor-acceptor triads having highly restricted conformations to study the effects of radical ion pair (RP) structure, energetics, and solvation on charge recombination. The chromophoric electron acceptor in these triads is a 4-aminonaphthalene-1,8-dicarboximide (6ANI), in which the 4-amine nitrogen atom is part of a piperazine ring. The second nitrogen atom of the piperazine ring is part of a para-substituted aniline donor, where the para substituents are X = H, OMe, and NMe(2). The imide group of 6ANI is linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) electron acceptor across a phenyl spacer in a meta relationship. The triads undergo two-step photoinduced electron transfer to yield their respective XAn(*)(+)-6ANI-Ph-NI(*)(-) RP states, which undergo radical pair intersystem crossing followed by charge recombination to yield (3)NI. Time-resolved electron paramagnetic resonance experiments on the spin-polarized RPs and triplet states carried out in toluene and in E-7, a mixture of nematic liquid crystals (LCs), show that for all three triads, the XAn(*)(+)-6ANI-Ph-NI(*)(-) RPs are correlated radical pairs and directly yield values of the spin-spin exchange interaction, J, and the dipolar interaction, D. The values of J are all about -1 mT and show that the LC environment most likely enforces the chair conformation at the piperazine ring, for which the RP distance is larger than that for the corresponding boat conformation. The values of D yield effective RP distances that agree well with those calculated earlier from the spin distributions of the radical ions. Within the LC, changing the temperature shows that the CR mechanism can be changed significantly as the energy levels of the RPs change relative to that of the recombination triplet.     

Development of a formulation of Pirodavir using 2-hydroxypropyl-β-cyclodextrin

Pirodavir, 4-[2-[1-(6-Methyl-3-pyridazinyl)-4-piperidinyl]ethoxy]benzoic acid ethyl ester, is an antiviral compound which has low aqueous solubility (<0.01 mg/ml). The compound is a weak base (pKa 5.8) with high lipophicity (logP 4.44). Ionization of the compound increases the solubility in acidic medium to 2.3 mg/ml at pH 2.4. However, a low pH is not acceptable for nasal application as this would induce irritation. Extensive solubility studies were performed using different types of substituted cyclodextrins in order to select an appropriate derivate capable of increasing solubility to an acceptable level for formulations for nasal application. Aqueous solubility of pirodavir increased in a linear fashion with increasing concentration of most of the substituted cyclodextrins. However, using 2-hydropropyl-β-cyclodextrin (HPBCD) the solubility increased in a non-linear fashion. Based on these studies HPBCD was selected as the most appropriate excipient. To support a clinical study on the treatment of rhinovirus cold by intranasal Pirodavir formulations were developed containing up to 5 mg/ml of pirodavir and up to 10% of HPBCD. Stability of the formulations was studied and found to be acceptable.     

A potent and highly selective sulfotransferase inhibitor

In the present work, we have used a newly developed, fluorescence-based assay to screen a library of >30 000 compounds as potential beta-arylsulfotransferase-IV inhibitors. A total of 11 inhibitors were discovered. Most of the compounds discovered showed low micromolar inhibition, but one of the compounds showed potent inhibition (Ki = 96 nM). The most potent of these inhibitors was tested against a variety of other purine binding enzymes and showed remarkable specificity.     

Controlling the magnetic ground state in Cr1-x Vx films

We demonstrate the ability to control the magnetic phase diagram of Cr1-x Vx(110) thin films grown on a W(110) substrate. Using angle-resolved photoemission, we have mapped paramagnetic and commensurate and incommensurate antiferromagnetic phases as a function of temperature, film thickness, and composition. We show that surface-localized electron states play a key role in the observed phase behaviors and suggest from this that it might be possible to control the magnetic phase by applying an external electric field.     

Preparation of α-terpineol and perillyl alcohol using zeolites beta

The preparation of α-terpineol by direct hydration of limonene catalyzed by zeolites beta was studied. The same catalyst was used to prepare perillyl alcohol by isomerization of β-pinene oxide in the presence of water. The aim was to optimize the reaction conditions to achieve high conversions of starting material and high selectivity to the desired products. In the case of limonene, it was found that the highest selectivity to α-terpineol was 88% with conversion of 36% under the conditions: 50 wt% of catalyst beta 25, 10% aqueous acetic acid (10 mL) (volume ratio limonene:H₂O?=?1:4.5), temperature 50 °C, after 24 h. In the case of β-pinene oxide, it was found that the highest selectivity to perillyl alcohol, which was 36% at total conversion, was obtained in the reaction under the following conditions: dimethyl sulfoxide as solvent (volume ratio β-pinene oxide:DMSO?=?1:5), catalyst beta 25 without calcination (15 wt%), demineralized water (molar ratio β-pinene oxide:H₂O?=?1:8), temperature 70 °C, 3 h. The present study shows that the studied reactions are suitable for the selective preparation of chosen compounds.