Indium(III) one-dimensional polymers with pyrazine and pyrazine, 2-carboxylic acid as the spacer molecules

The reactions of indium(III) chloride tetrahydrate with pyrazine (C₄H₄N₂) and pyrazine, 2-carboxylic acid afford two polymeric frameworks, the structures of which were characterized in the solid state by single crystal analysis. The former is a one-dimensional infinite structure interlinked by the pyrazine spacer, while the latter is a one-dimensional ‘zigzag’ polymeric structure. A dimeric indium(III) pyrazine complex is also reported.     

Novel tocopheryl compounds. Part 16: Nitration of α-tocopheryl acetate—a mechanistic study

The reaction of α-tocopheryl acetate (vitamin E acetate, 3) with concentrated nitric acid proceeds according to a non-radical, two-step mechanism, producing 5-nitromethyl-γ-tocopheryl acetate (4) in good yields. In the first step, oxidation of 3 affords a benzylic cation intermediate (8), which in the second step adds nitrite to give 4. The acetyl group, which stabilizes intermediate 8 intramolecularly, remains bound to the tocopheryl moiety throughout the reaction.     

Non-linear calibration functions in ion chromatography with suppressed conductivity detection using hydroxide eluents

The linearity of calibration curves in ion chromatography with suppressed conductivity detection using hydroxide eluents was investigated. Theoretical calibration curves were derived for strong electrolytes and weak monobasic acids and the results compared with experimental data. At low concentrations up to 1 micromol l(-1) the autoprotolysis of water induces left-curved calibration functions even for strong electrolytes like nitrate. The experimental data are best described by a quadratic function, the differences between linear and quadratic regression being up to 10%. At higher concentrations the calibration curves for strong electrolytes are linear. Due to incomplete dissociation, the calibration curves for weak mono- and dibasic acids show a right curvature. Thus, depending on the analyte and the concentration range of interest, analysts should carefully choose between a linear and a quadratic regression function.     

Sampling and metrology

The result of a measurement refers in principle only to the amount of substance actually contributing to the analytical signal. However, an appropriate definition of the measurand must include a specification of the system for which the result of the measurement should apply. All systems being inherently heterogeneous, representativity assumes importance for the metrological quality of a measurement, and the process needed to ascertain representativity is sampling. The contribution from this characteristic must be included when expressing the uncertainty of the reported value of the measurand. Representative sampling of systems that are infinite or non-uniform was developed by Pierre Gy in his Theory of Sampling. Finite systems can achieve uniformity by mechanical treatment and mixing; the heterogeneity of these systems can be characterized by a sampling constant, expressed in units of weight, for each particular species being determined. Examples of the contribution of sampling to the uncertainty of analytical results are discussed for some biological materials. Presented at the 2nd International Conference on Metrology – Trends and Applications in Calibration and Testing Laboratories, November 4–6, 2003, Eilat, Israel.     

On the bond-stretch isomerism in the benzo[1,2:4,5]dicyclobutadiene system--an ab initio MR-AQCC study.

Bond-stretch isomerism in benzo[1,2:4,5]dicyclobutadienle (BDCB) has been investigated using the MR-AQCC/6-31G(d) method, a high-level multireference ab initio approach including size-extensivity corrections. The applied theoretical approach includes both nondynamical and dynamical electron correlation effects. Full MR-AQCC geometry optimizations of localized (1) and delocalized (3) isomers as well as the transition structure (TS) have been determined using D2h, symmetry restriction. The calculations show that both isomers are approximately of equal stability separated by a barrier with a height of about 5 kcal mol(-1). Thus, the present results strongly indicate that benzof[1,3:4,5]dicyclobutadiene is a very good candidate for an organic compound exhibiting bond-stretch isomerism, since isomers 1 and 3 correspond to true minima on the double-well potential energy surface, which are separated by a sufficiently high barrier. It is particularly important to emphasize that isomer 3 represents a realization of the highly elusive quasi-[10]annulene.     

Application of Graphite-Epoxy Composite Electrodes in Differential Pulse Anodic Stripping Voltammetry of Heavy Metals

An analytical study on the use of graphite-epoxy composite (GEC) electrodes for differential pulse anodic stripping voltammetry (DPASV) of heavy metals is presented. This study is accompanied by microscopic observations of the electrode surface before and after the stripping step in comparison to glassy carbon electrode. GEC electrodes show much better accumulation properties and consequently acceptable behaviour which makes them suitable as working electrodes in the DPASV of heavy metals. Lead determination in real water samples in a batch system as well as some preliminary results in a flow-through system are presented. The detection limits in batch measurements were 100ppb for Cd, 10pb for lead and 50ppb for copper. The detection limit for lead in the flow-through system was similar to that in the batch. The results obtained show that these low cost and easy to prepare materials can be of interest in future research concerning stripping techniques of heavy metals and other analytes.     

Preparation and characterization of fused-silica capillary columns coated with <Emphasis Type="Italic">m</Emphasis>-carborane–siloxane copolymers for gas chromatography

The carborane–siloxane copolymers Dexsil 300, a 34.5% bis(dimethylsilyl)-m-carborane–65.5% dimethylsiloxane copolymer, and Dexsil 400, a 24.9% bis(dimethylsilyl)-m-carborane–50.8% dimethyl, 24.3% methylphenylsiloxane copolymer, were coated on fused silica capillary columns and their gas chromatographic properties were evaluated. Their selectivity was evaluated using both Rohrschneider–McReynolds constants and triacylglycerol indices. The bis(dimethylsilyl)-m-carborane unit turned out to be equivalent to two dimethylsiloxy units and one half of a diphenylsiloxy unit. The m-carborane unit was found to cause a 15–25 K shift in the elution temperature between 120 and 360 °C. The working range was from 20 and 0 °C to 380 °C for Dexsil 300 and Dexsil 400, respectively. The column bleeding levels at 380 °C were below 20 and 15 pA for Dexsil 300 and Dexsil 400, respectively.     

Ganglioside analysis by thin-layer chromatography matrix-assisted laser desorption/ionization orthogonal time-of-flight mass spectrometry

Metastable decomposition of ions generated in matrix-assisted laser desorption/ionization (MALDI) mass spectrometers complicates analysis of biological samples that have labile bonds. Recently, several academic laboratories and manufacturers of commercial instruments have designed instruments that introduce a cooling gas into the ion source during the MALDI event and have shown that the resulting vibrational cooling stabilizes these labile bonds. In this study, we compared stabilization and detection of desorbed gangliosides on a commercial orthogonal time-of-flight (oTOF) instrument with results we reported previously that had been obtained on a home-built Fourier transform mass spectrometer. Decoupling of the desorption/ionization from the detection steps resulted in an opportunity for desorbing thin-layer chromatography (TLC)-separated gangliosides directly from a TLC plate without compromising mass spectral accuracy and resolution of the ganglioside analysis, thus coupling TLC and oTOF mass spectrometry. The application of a declustering potential allowed control of the matrix cluster and matrix adduct formation, and, thus, enhanced the detection of the gangliosides.     

Proton affinity of β-oxalylaminoalanine (BOAA): Incorporation of direct entropy correction into the single-reference kinetic method

A new version of the single-reference-extended kinetic method is presented in which direct entropy correction is incorporated. Results of calibration experiments with the monodentate base pyridine and the bidentate base ethylenediamine are presented for which the method provides proton affinities in excellent agreement with published values and reasonable predictions for the protonation entropies. The method is then used to determine the proton affinity and protonation entropy of the non-protein amino acid beta-oxalylaminoalanine (BOAA). The PA of BOAA is found to be 933.1 +/- 7.8 kJ/mol and a prediction for the protonation entropy of -39 J mol(-1) K(-1) is also obtained, indicating a significant degree of intramolecular hydrogen bonding in the protonated form. These results are supported by hybrid density functional theory calculations at the B3LYP/6-311++G**//B3LYP/6-31+G* level. They indicate that the preferred site of protonation is the alpha-nitrogen atom (PA = 935.0 kJ/mol) and that protonated BOAA has a strong hydrogen bond between the hydrogen on the alpha-amino group and one of the carbonyl oxygen atoms on the side chain.