Retention of β blockers on native titania stationary phase

In recent years, metal oxides such as titania have been commercially available as chromatographic beds that can potentially be used to achieve novel separations of polar compounds. For example β blockers, which are more often encountered in environmental sciences, have a wide range of polarity, and their basic character leads to difficult sample treatment and separation on conventional silica‐based sorbents. The contribution of titania to the selective analysis of nine β blockers was evaluated in terms of retention mechanisms observed in hydrophilic interaction LC using acetonitrile/water mobile phases with various additives. The mobile phase additives enabled to control the β blocker charge as well as the titania surface charge. Depending on their respective ionic state, various retention mechanisms were identified at low water contents (<40%), including mainly adsorption mixed with hydrophilic interaction LC partition, ion exchange and ion exclusion. An unexpected retention was also observed for high water content and high pH, changing the selectivity of the support.     

Corrosion of gadolinium and ytterbium in LiCl-KCl melt

Corrosion of gadolinium and ytterbium in a molten eutectic mixture of lithium and potassium chlorides is studied in the present work using the gravimetry and EMF methods. It is found that the corrosion rate of ytterbium is 3–5 times higher than that of gadolinium under similar conditions. Satisfactory agreement between the current density values of gadolinium corrosion calculated on the basis of the results of the gravimetric data and the values of steady-state potentials points to the electrochemical mechanism of gadolinium corrosion in the LiCl-KCl melt.     

Synthesis of hydroxyethylhydrazine by the Raschig process and comparison with synthesis by the alkylation process

The Raschig synthesis of hydroxyethylhydrazine (HEH) is studied, that is, the reaction of monochloramine on ethanolamine. The formation of HEH is monitored by UV spectrometry, and the influence of temperature and pH is studied. The primary reaction is an SN₂‐type mechanism, whereas the main secondary reaction is the oxidation of HEH by monochloramine. This reaction is also monitored by UV spectrometry, and the oxidation product is identified by GC–MS analysis, showing the formation of hydroxyethylhydrazone. The reaction mechanisms and the rate constants were determined, and the results permit establishing the main reactions occurring during HEH synthesis. These reactions were validated in a concentrated medium, with the systematic study of the influence of the molar ratio p ([HEH]₀/[NH₂Cl]₀) and the final sodium hydroxide concentration and temperature. A comparison is made with the other synthesis process already published, that is, the alkylation of hydrazine by either chloroethanol or epoxide. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 331–344, 2011     

Selective monodeoxygenation of quinoxaline-amino acid and ester dioxides

Trimethyl phosphite selectively removes the N-1-oxygen in N-(3-methyl-2-quinoxaloyl) L-α-amino ester-1,4-dioxides, whereas it removes the N-4-oxygen in the corresponding series of dioxides lacking the C₃-Me. This selectivity reversal reflects the relative strength of the intrahydrogen-bridging to the N-1-oxygen. The monoxides having the favourable N-oxygen are not reduced to the quinoxalines, implying that the reagent requires doubling of the N-oxide function for deoxygenation. However, alkaline sodium dithionite removes the N-1-oxygen in both series of the amino acid-dioxides, as well as in the parent quinoxaline-2-carboxylic acid-dioxides, a result that contradicts the report stating removal of the N-4-oxygen. The N-oxygenated quinoxalinium ion ($\text{m}\text{e}$ 145 or 159) prevails in the MS of the 4-oxides, but it is not observed (<1%) for the isomeric 1-oxides. ¹H NMR, ¹³C NMR and UV spectral data also offer diagnostic criteria for differentiation between the isomeric 1- and 4-oxides. Aryl-heteryl “interaction” (as revealed by ¹H NMR, though not by ¹³C NMR in the aromatic amino ester dioxides) is not manifested in the corresponding monoxides.     

Lithium diorganocuprate reactions with l-serine derivatives

The lithium diorganocuprate reactions with L-serine derivatives are studied. Retention of configuration, or at least a high enantiomeric excess (>80%) of the formed α-amino esters is observed in all cases. Attempts are made to restrict side-reactions.     

Polarographic reduction and tautomeric structure of 2-amino-5-arylazothiazoles

The polarographic behaviour of a series of 2-amino-4-phenyl-5-arylazothiazoles has been investigated at a dropping mercury electrode. Each of the compounds studied exhibits one wave which was shown to correspond to the reductive cleavage of the azo linkage by a 4e irreversible step. On the basis of the polarographic data, it was concluded that the compounds exist only in one tautomeric form, namely the aminoazo structure 1 . The results of E_1/2 — σ_X correlations and HMO calculations of bonding energies of the various possible tautomeric forms 1–3 indicate that the aminoazo form 1 is the most stable structure of the compounds examined.     

Electronic and magnetic structures of V-doped zinc blende Zn1-xVxNyO1-y and Zn1-xVxPyO1-y

Electronic and magnetic structures of zinc blende ZnO doped with V impurities are studied by first-principles calculations based on the Korringa-Kohn-Rostoker (KKR) method combined with the coherent potential approximation (CPA).Calculations for the substitution of O by N or P are performed and the magnetic moment is found to be sensitive to the N or P content.Furthermore,the system exhibits a half-metallic band structure accompanied by the broadening of vanadium bands.The mechanism responsible for ferromagnetism is also discussed and the stability of the ferromagnetic state compared with that of the paramagnetic state is systematically investigated by calculating the total energy difference between them by using supercell method.     

Star factorizations of graph products

A k‐star is the graph K_1,k. We prove a general theorem about k‐star factorizations of Cayley graphs. This is used to give necessary and sufficient conditions for the existence of k‐star factorizations of any power (K_q)^s of a complete graph with prime power order q, products C × C ×··· × C of k cycles of arbitrary lengths, and any power (C_r)^s of a cycle of arbitrary length. © 2001 John Wiley & Sons, Inc. J Graph Theory 36: 59–66, 2001