Reduction of nitric oxide,nitrous acid and nitrogen dioxide at platinum electrodes in acidic solutions: Review and new voltammetric results

The literature concerning the chemical and electrochemical reactions of nitric oxide, nitrous acid and nitrogen dioxide in aqueous solutions is reviewed briefly, with emphasis on electrochemical reductions at platinum electrodes in acidic solutions. The voltammetric behavior of NO and NO₂ at a Pt electrode in perchloric acid is virtually identical to that for HNO₂ and this is explained on the basis of a common electroactive precursor concluded to be NO⁺. Three cathodic waves are obtained for acidic solutions of NO, HNO₂ and NO₂. The first two waves correspond to reduction of NO⁺ to NO and N₂O₃ to NO, respectively. The presence of N₂O₃ results from decomposition of the parent compounds. The presence of Br^- or Cl^- in acidic solutions of the title compounds promotes the voltammetric reductions at lower H⁺ concentrations. This probably results from formation of electroactive nitrosyl halides.     

Classification of gasoline data obtained by gas chromatography using a piecewise alignment algorithm combined with feature selection and principal component analysis

A fast and objective chemometric classification method is developed and applied to the analysis of gas chromatography (GC) data from five commercial gasoline samples. The gasoline samples serve as model mixtures, whereas the focus is on the development and demonstration of the classification method. The method is based on objective retention time alignment (referred to as piecewise alignment) coupled with analysis of variance (ANOVA) feature selection prior to classification by principal component analysis (PCA) using optimal parameters. The degree-of-class-separation is used as a metric to objectively optimize the alignment and feature selection parameters using a suitable training set thereby reducing user subjectivity, as well as to indicate the success of the PCA clustering and classification. The degree-of-class-separation is calculated using Euclidean distances between the PCA scores of a subset of the replicate runs from two of the five fuel types, i.e., the training set. The unaligned training set that was directly submitted to PCA had a low degree-of-class-separation (0.4), and the PCA scores plot for the raw training set combined with the raw test set failed to correctly cluster the five sample types. After submitting the training set to piecewise alignment, the degree-of-class-separation increased (1.2), but when the same alignment parameters were applied to the training set combined with the test set, the scores plot clustering still did not yield five distinct groups. Applying feature selection to the unaligned training set increased the degree-of-class-separation (4.8), but chemical variations were still obscured by retention time variation and when the same feature selection conditions were used for the training set combined with the test set, only one of the five fuels was clustered correctly. However, piecewise alignment coupled with feature selection yielded a reasonably optimal degree-of-class-separation for the training set (9.2), and when the same alignment and ANOVA parameters were applied to the training set combined with the test set, the PCA scores plot correctly classified the gasoline fingerprints into five distinct clusters.     

Potential of electrophilic epoxide reactions for the monitoring of acid gases in the environment

Mineral and short-chain carboxylic acid vapours and NO(x) gases were reacted with cyclohexene oxide (1,2-epoxycyclohexane) to quantitatively produce specific, thermally stable cyclohexyl derivatives. Subsequent analysis of these derivatives by gas chromatography with mass spectroscopy and flame ionisation detection afforded a multi analyte method for the assay of these gaseous acidic atmospheric species. Derivatisation was found to be quantitative for the derivatives tested and the method highly sensitive (to 0.3 mg/m3 for a 30 l sample), accurate, precise and free from apparent interferences. The technique has been applied to "acid stack gases" and a number of other acid rich atmospheres and the results obtained show good agreement with the single analyte wet chemical determinations indicating that the approach has considerable potential as a routine analytical method for measuring such atmospheric pollutants. The high specificity of the reaction mechanism and its potential for the analysis of analyte mixtures is illustrated in the assay of nitric acid and its acid anhydride, dinitrogen pentoxide.     

A Bloembergen–Purcell–Pound <Superscript>13</Superscript>C NMR relaxation study of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound ¹³C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T ₁) and the rates (R ₁=1/T ₁) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion.     

Studies on azaspiracid biotoxins. I. Ultrafast high-resolution liquid chromatography/mass spectrometry separations using monolithic columns

In this study, the performance of monolithic columns was evaluated for ultrafast liquid chromatography/mass spectrometry (LC/MS) analyses and for high-resolution separations of several azaspiracid biotoxin analogs. Because of their high permeability, monolithic columns offer a number of advantages over conventional packed columns; viz., very low backpressures and relatively flat van Deemter curves at high flow rates. That is, very high flow rates can be used for ultrafast analyses or, by using longer than normal columns, high-resolution separations are possible. In a series of experiments, we varied the mobile phase flow rates between 1 and 8 mL/min, and studied their impact on chromatographic parameters such as retention time, resolution, number of plates and pressure. The chromatographic run times could be reduced to ca. 30 s without a significant change in the separation efficiency. A signal intensity comparison revealed interesting differences between atmospheric-pressure chemical ionization (APCI) and electrospray ionization (ESI) in their flow-rate dependency. An explanation with respect to the behavior as of a mass-flow or a concentration-dependent device is given in the paper. Additionally, the column length was varied between 10 and 70 cm. As a result, the number of theoretical plates increased substantially. In the example shown in the report, an increase from 13 000 plates for a 10-cm column to 80 000 for a 70-cm column is demonstrated. In addition, the potential of the monolithic columns for high-resolution LC/MS separations is shown for a complex biotoxin mixture, which was separated on a 40-cm-long column.     

ELLIPSOMETRY OF BLACK LIPID MEMBRANES OF EGG LECITHIN AND CHLOROPLAST EXTRACTS

Abstract— Ellipsometric angles and reflectivity of black lipid membranes containing either egg lecithin or chloroplast extracts were measured at a wavelength of 6328 Å. Evidence was found for positive uniaxial anisotropy in membranes of lecithin. If the thickness of those films is assumed to be 62 Å, the refractive index normal to the film surface is 1.471 ± 0.004, and the refractive index parallel to the film surface is 1.454 ± 0.003. The results for membranes of chloroplast extracts also indicate a positive anisotropy in the indices of absorption.     

High-speed peak matching algorithm for retention time alignment of gas chromatographic data for chemometric analysis

A rapid retention time alignment algorithm was developed as a preprocessing utility to be used prior to chemometric analysis of large datasets of diesel fuel profiles obtained using gas chromatography (GC). Retention time variation from chromatogram-to-chromatogram has been a significant impediment against the use of chemometric techniques in the analysis of chromatographic data due to the inability of current chemometric techniques to correctly model information that shifts from variable to variable within a dataset. The alignment algorithm developed is shown to increase the efficacy of pattern recognition methods applied to diesel fuel chromatograms by retaining chemical selectivity while reducing chromatogram-to-chromatogram retention time variations and to do so on a time scale that makes analysis of large sets of chromatographic data practical. Two sets of diesel fuel gas chromatograms were studied using the novel alignment algorithm followed by principal component analysis (PCA). In the first study, retention times for corresponding chromatographic peaks in 60 chromatograms varied by as much as 300 ms between chromatograms before alignment. In the second study of 42 chromatograms, the retention time shifting exhibited was on the order of 10 s between corresponding chromatographic peaks, and required a coarse retention time correction prior to alignment with the algorithm. In both cases, an increase in retention time precision afforded by the algorithm was clearly visible in plots of overlaid chromatograms before and then after applying the retention time alignment algorithm. Using the alignment algorithm, the standard deviation for corresponding peak retention times following alignment was 17 ms throughout a given chromatogram, corresponding to a relative standard deviation of 0.003% at an average retention time of 8 min. This level of retention time precision is a 5-fold improvement over the retention time precision initially provided by a state-of-the-art GC instrument equipped with electronic pressure control and was critical to the performance of the chemometric analysis. This increase in retention time precision does not come at the expense of chemical selectivity, since the PCA results suggest that essentially all of the chemical selectivity is preserved. Cluster resolution between dissimilar groups of diesel fuel chromatograms in a two-dimensional scores space generated with PCA is shown to substantially increase after alignment. The alignment method is robust against missing or extra peaks relative to a target chromatogram used in the alignment, and operates at high speed, requiring roughly 1 s of computation time per GC chromatogram.