Feasibility study for the preparation of certified reference materials part I – mineral oil contaminated soils

The international joint project HYCREF (Contract No. G6RD-CT-2002-00854), funded by the European Commission in the 5th Framework programme, aimed to develop methods to prepare homogeneous and stable reference materials of water, soil, and waste contaminated with mineral oil hydrocarbons and to certify the mineral oil content by gas chromatographic methods. The results of a feasibility study for the preparation of three soil reference materials are discussed in this paper, and for the preparation of three waste reference materials in the second part (Koch et al., Accred Qual Assur submitted for publication). The soil materials were selected to represent different soil types and contamination levels. The project plan set three requirements for these reference materials: uncertainty in the mineral oil content resulting from the certification exercise <5%, a sample inhomogeneity of <3% and a minimum long-term stability of 5 years. For the most part, these requirements were met within this project.     

Mass spectrometric study of some cycloalkane/ene-condensed 2-thioxo-2935556-pyrimidin-4(1H)-ones and cycloalkane/ene-condensed [l,3] thwzino [3,2-a]-pyrimidinones under electron impact

The mass spectra of four cycloalkane/ene cis- and trans-condensed 2-thioxo-2,3,5,6-tetrahydropyrimidin-4(1H)-ones and the corresponding cycloalkane/ene cis- and trans-condensed [l,3]thiazino[3,2-a]pyrimidinones were measured. Fragmentation pathways were confirmed by metastable ion analyses and exact mass measurements. The bicyclic isomers were easy to distinguish from each other, whereas the corresponding tricyclic isomeric adducts gave fairly similar mass spectra, owing to their favoured reiro-Diels- Alder fragmentations accompanied by the migration of one or two hydrogen atoms.     

Electron ionization mass spectra of some norbornane/ene-fused 2-N-phenyliminoperhydro-1,3-oxazines

The 70 eV electron ionization (EI) mass spectra were recorded for eight norbornane/ene-fused 2-N-phenyl-iminoperhydro-1,3-oxazines, and the fragmentation patterns were studied by metastable ion analysis and exact mass measurement. Whereas the stereoisomeric unsaturated compounds could not be distinguished on the basis of their EI mass spectra, the stereoisomeric saturated compounds gave rise to clearly different spectra. The ionized unsaturated compounds decomposed mainly by two consecutive retro-Diels-Alder (RDA) reactions. A methyl substituent on the ring nitrogen strongly influenced the charge distribution on the RDA fragments. The ionized saturated compounds fragmented through several pathways. Loss of cyclopentadiene from the molecular ion was the energetically favoured fragmentation reaction for the saturated di-endo-fused compounds but was unimportant for the di-exo-fused compounds.     

Electrospray ionization mass spectrometric studies of nucleophilic carbenes derived from pyrazolium and indazolium carboxylates

Pyrazolium-3-carboxylate and indazolium-3-carboxylate, which belong to the class of pseudo-cross-conjugated mesomeric betaines and which represent the electronically relevant partial structures of the betaine alkaloid Nigellicin, were examined by electrospray ionization mass spectrometry. These compounds decarboxylate to pyrazol-3-ylidene and indazol-3-ylidene. The formation of adducts of these new nucleophilic carbenes under the measurement conditions was examined.     

Electron impact and isobutane and ammonia chemical ionization mass spectrometry of some tetrahydropyranyl acetals

The electron impact induced fragmentations of 24 tetrahydropyrane ethers of different types of alcohols were studied by exact mass measurement and metastable ion analysis. The most characteristic features of the spectra were associated with the tetrahydropyrane ring, As the size of the molecule increased, the fragmentations with respect to exocyclic oxygen became more important allowing differentiation among the isomeric aliphatic alcohols. Under isobutane chemical ionization, loss of neutral alcohol from [M + H]⁺ leading to the formation of a tetrahydropyranium ion was dominant for aliphatic alcohol derivatives, whereas loss of 2-hydroxy tetrahydropyrane giving rise to an alkyl ion was dominant for bicyclic alcohol derivatives. Under ammonia chemical ionization, nucleophilic substitution reactions were always most important.     

Effects of functional group interactions in the chemical ionization mass spectra of some substituted cis-1,3-cyclopentane dicarboxylic acids and their derivatives

Ammonia, isobutane and methane chemical ionization mass spectra have been measured for some substituted cis-1,3-cyclopentane dicarboxylic acids and their derivatives. The relative proton affinities of the different functional groups determine the protonation site in the molecule and thereby greatly affect the fragmentation. Intramolecular catalysis clearly facilitates the elimination of water in cases where functional groups can interact with each other.     

Saturated heterocycles. 251 . Determination of σ+ values of heteroaryl-substituted phenyl groups via ring-chain tautomerism

The Hammett-Brown electrophilic substituent constants σ⁺ for five heteroaryl-substituted phenyl groups were estimated via the ring-chain tautomeric equilibria of three sets of oxazolidines and 1,3-oxazines in deuteriochloroform solution. For oxazolidines derived from norephedrine and norpseudoephedrine, the σ⁺ values were also determined via the gas-phase ring-chain equilibria, by means of mass spectrometry. The results show that the heteroaromatic substituents studied have a slight electron-withdrawing character, with σ⁺ in the range -0.03 to 0.59. The gas-phase σ⁺ values are significantly higher than the solution values.     

Ammonium ion mediated resorcarene capsules: ESI-FTICRMS study on gas-phase structure and ammonium ion affinity of tetraethyl resorcarene and its per-methylated derivative

The ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of carbon chain of the ammonium cation facilitated the complex formation until the sterical hindrance impeded the complexation. Dimeric as well as monomeric ammonium ion complexes were formed with resorcarene 1, but resorcarene 2 was unable to form the dimeric capsules because of the lack of H-bond donor possibilities. The nature of binding of the guest was further investigated with ion-molecule reactions and by determination of the single crystal X-ray structure of host 1 complexed with tetramethyl ammonium bromide.     

Fast gas chromatography-negative-ion chemical ionization mass spectrometry with microscale volume sample preparation for the determination of benzodiazepines and alpha-hydroxy metabolites, zaleplon and zopiclone in whole blood

Fast gas chromatography/negative-ion chemical ionization mass spectrometric (GC/NICI-MS) assay combined with rapid and nonlaborious sample preparation is presented for the simultaneous determination of benzodiazepines and alpha-hydroxy metabolites, zaleplon and zopiclone in whole blood. The compounds were extracted from 100 microl of whole blood by simultaneous multitube, microscale liquid-liquid extraction (LLE) and derivatized by N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), without the need for the time-consuming concentration stage. In the analytical separation, various parameters of fast GC/NICI-MS were applied, e.g. the use of hydrogen as a GC carrier gas, a high carrier gas velocity, a small film thickness of the analytical column, fast MS data acquisition, fast temperature ramping, and high initial and final temperatures of GC column. Sensitive identification, screening and quantitation of 18 compounds of interest were achieved in chromatographic separation in only 4.40 min. Accurate and reproducible results were obtained by using five different and carefully selected deuterated analogues on the basis of the chemical properties of the target analytes. Nevertheless, for alpha-OH-midazolam, and for bromazepam and flunitrazepam at low concentrations, the results can be considered only semiquantitative on the basis of the validation data. The extraction efficiencies ranged from 74.3 to 105.7% and the limits of quantitation (LOQ) from 1 to 100 ng ml(-1). Rapid sample preparation and fast chromatographic separation allowed cost-efficient, reliable and high sample-throughput analyses with a low amount of manual work. The method was fully validated and accredited according to EN ISO/IEC 17025 standards and is applicable for sensitive, reliable and quantitative determination of benzodiazepines, zaleplon and zopiclone, e.g. in clinical and forensic toxicology.     

The influence of nucleus density on optical properties in nucleated isotactic polypropylene

The effect and efficiency of three nucleating agents, a sorbitol based clarifier, a traditional heterogeneous nucleating agent and poly(vinylcyclohexane) (PVCH) was studied in polypropylene (iPP) homopolymer. The nucleating agents were added to iPP in different amounts; PVCH in 0–200 ppm, while the other two in 0–2000 ppm. Optical and mechanical properties were determined on injection molded plates or bars, respectively. Nucleation efficiency was studied by thermal analysis, while structure was characterized by polarized light (PLM), scanning electron (SEM) and atomic force microscopy (AFM). Nucleus density was calculated using the method of Lamberti, which is based on the kinetic theory of the crystallization developed by Lauritzen and Hoffmann. The results proved that the nucleating agents modify properties in different ways and extent. PVCH is very efficient already at small concentrations and increases the stiffness of iPP considerably more than the other two compounds. On the other hand, the clarifier and the traditional nucleating agent induce better optical properties even at smaller efficiency. The structure developing in the presence of the three nucleating agents is also different. The clarifier forms a network in iPP and induces the formation of a microcrystalline structure according to the former literature data. Microspherulitic structure develops in the presence of the heterogeneous nucleating agent studied, while relatively large supermolecular units form in iPP nucleated by PVCH even under the conditions of injection molding. The calculation of nucleus density by existing models and the comparison of the results to optical properties proved that haze is determined by the size of the supermolecular units of the polymer and this latter depends on nucleus density.