Speciation of halogenides and oxyhalogens by ion chromatography-inductively coupled plasma mass spectrometry

A speciation method utilizing ion chromatography coupled with inductively coupled plasma mass spectrometry is described for simultaneous analysis of eight halogenides and oxyhalogens: chloride, chlorite, chlorate, perchlorate, bromide, bromate, iodide and iodate. The method was applied for the analysis of drinking water samples collected from water treatment plants in areas in Finland, which are known to have high bromine concentrations in ground water. Water samples collected before and after disinfection were analyzed to get information about potential species conversion as a result of purification. Chloride and chlorate were the chlorine species found in these water samples, and iodine existed as both iodate and iodide. In the case of bromine, species conversion had taken place, since total bromine concentrations were increased during disinfection but bromide concentrations were decreased. No bromate was observed in the samples. The detection limits for all the chlorine species studied were 500 μg/l, for bromine species studied 10 μg/l, for iodide 0.1 μg/l and for iodate 0.2 μg/l.     

Determination of organic acids in wine by zone electrophoresis on a chip with conductivity detection

An appropriate combination of separation mechanisms (simultaneous use of differences in pK values, host-guest complexations, and the ionic strength dependences of the actual ionic mobilities) provided zone electrophoresis (ZE) resolution of 22 organic and inorganic acids expected in wines on a polymethylmethacrylate (PMMA) chip with integrated conductivity detection. These separating conditions offered a framework for the ZE determination of organic acids responsible for some important organoleptic characteristics of wines (tartrate, malate, succinate, acetate, citrate, and lactate). The ZE procedure developed in this context is simple and rapid (ca. 10 minutes' analysis time), while affording reproducible migration and quantitation data for the acids. For example, 0.8-2.0% RSD values characterized the migration times of the acids for 25 repeated ZE runs with the same sample carried out in 5 days in the background electrolyte solution prepared freshly on a daily basis, while 3-5% RSD values were typical for the accompanying peak area data. The concentration ranges within which the acids of analytical interest could be determined in one ZE run covered all wine samples included in our study (100-400-fold sample dilutions were needed to work under the conditions corresponding to the validities of the calibration data). 90-110% recoveries of the acids as obtained repeatedly for one of the reference wine samples used in our experiments indicate a good predisposition of the present method to provide accurate analytical results. This statement also supports the results from the determination of the acids in reference wine samples with claimed concentrations of malic (five samples), tartaric (one sample), and lactic (one sample) acids.     

Ring transformation of 1,5-benzoxazepines into spirobenzoxazoles. Synthesis of pyrazolo[1′,5′:3,4][1,2,4]triazino-[5,6-b][1,5]benzoxazepines and spiro[benzoxazole-2′(3′H),4(1H)-pyrazolo[5,1-c][1,2,4]triazines]

The reactions of the 3-substituted 4-amino-8-ethoxycarbonyl[5,1-c][1,2,4]triazines 1 and 2 with o-amino-phenol hydrochloride gave the pyrazolo[1′,5′:3,4][1,2,4]triazino[5,6-b][1,5]benzoxazepines 5 and 8 . The alkylation of 5 with methyl iodide and isopropyl iodide afforded the 6-alkoxylpyrazolo[1′,5′:3,4][1,2,4]triazino-[5,6-b][1,5]benzoxazepines 6a and 6b , respectively. Refluxing of 5, 6a, 6b and 8 in hydrochloric acid/acetic acid resulted in ring transformation to produce the spiro[benzoxazole-2′(3′H),4(1H)pyrazolo[5,1-c][1,2,4]-triazines] 7a, 7b and 9 . The screening data of the above compounds was described.     

Use of selective extraction and fast chromatographic separation combined with electrophoretic methods for mapping of membrane proteins

A model system for selective solubilization and fast separation of proteins from the rat liver membrane fraction and purified rat liver plasma membranes for their further proteomic analysis is presented. For selective solubilization, high-pH solutions and a concentrated urea solution, combined with different detergents, are used. After extraction, proteins are separated by anion-exchange chromatography or a combination of anion- and cation-exchange chromatography with convective interaction monolithic supports. This separation method enables fast and effective prefractionation of membrane proteins based on their hydrophobicity and charge prior to one-dimensional (1-D) and 2-D electrophoresis and mass spectrometry. By use of this sample preparation method, the less-abundant proteins can be detected and identified.     

Capillary zone electrophoresis in methanol: migration behavior and background electrolytes

Nonaqueous (NA) solutions are often used as background electrolytes (BGEs) and NA solvents are added to aqueous BGEs as organic modifiers in capillary zone electrophoresis (CZE), in order to optimize the separations. This can be tricky, however, because the pH* and pK* concepts may be totally different in NA solvents, whereas often less knowledge is available concerning phenomena, such as system zones, applying NA solvents. In this paper, the concepts of pH* and pK* are considered for methanol as a solvent and pK* values are determined for several components in mixtures of water and methanol. With a mathematical model, adapted for calculations in methanol, parameters are calculated describing the fronting or tailing character of peaks and the question of peaks or dips, and the existence of system zones is discussed for pure methanol as a solvent. These aspects are experimentally verified, applying BGEs useful for the separation of cationic species in the indirect UV mode. It can be concluded that the mathematical model developed for aqueous BGEs is applicable to BGEs in methanol, too, and that the behavior of BGEs in methanol is comparable with that in water concerning the fronting or tailing character of peaks and the question of peaks and dips, although the mobilities and pK values can change significantly.     

Crystal structures of 2-(2-methoxyphenyl) perimidine and its hemihydrate

The crystal structures of the title compound and that of its hemihydrate have been determined. The anhydrous compound is roughly planar due to an intramolecular hydrogen bond (IMHB). The orange color can be related to its planarity and to the greater degree of overlapping between the perimidine and the phenyl group than in the hemihydrate. The yellow hemihydrate is not planar and the water molecule joins through O-HN hydrogen bonds two molecules related by a crystallographic twofold axis. In solution the compound behaves like the anhydrous form.     

Tosylation and acylation of cellulose in 1-allyl-3-methylimidazolium chloride

Tosylation and acylation of cellulose were performed under mild reaction conditions using imidazolium based ionic liquids (ILs) as solvents. The non-degradative nature, lower viscosity, as well as higher solubility of cellulose in [amim]Cl encouraged us to carry out the reactions in this media. The reactions described here were optimised for this particular solvent in order to obtain different cellulose derivatives with high yields, homogeneity and degree of substitution (DS). Two reagents employed for the in situ activation of carboxylic acids were N,N′-carbonyldiimidazole (CDI) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide hydrochloride (EDCI). Final products were characterised by solution and solid-state NMR techniques. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis of a [60]fullerene‐functionalized poly(vinyl chloride) derivative by stereospecific chemical modification of PVC

The covalent attachment of [60]fullerene (C₆₀) to two poly(vinyl chloride) (PVC) samples with different isotactic content is achieved by direct reaction in o‐dichlorobenzene (o‐DCB) solution in the presence of AIBN. The extent of fullerenation is controlled by varying the C₆₀ feed ratio. The pendant C₆₀‐chemically modified PVC polymers are soluble in tetrahydrofuran (THF) and have been characterized by UV–vis, NMR, FTIR, DSC, TGA, cyclic voltammetry, and SEM. The quantitative microstructural analysis after covalent attachment of the bulky C₆₀ moiety to the PVC has been followed by ¹³C NMR spectroscopy. From the results it can be concluded that the modification of PVC by graft reaction through free radical reaction proceeds by a stereoselective mechanism. This conclusion has been confirmed on the basis of the increase of the glass‐transition temperature (T_g) and the thermal stability of the C₆₀‐chemical modified PVC samples. The fullerenated PVCs obtained show good electron acceptor properties, as evidenced by electrochemical investigations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5408–5419, 2007