Quality assurance in daily practice

 A report based on the workshop on "Quality Assurance in Daily Practice", organised by the study group "Quality Assurance and Accreditation" from the Division of Analytical Chemistry of the Federation of European Chemical Societies (SGQAA/DAC/FECS) held at the EUROANALYSIS-10 conference in Basle, 6–11 September 1998.     

31P NMR as a tool for studying incorporation of Ni, Co, Fe, and Mn into aluminophosphate zeotypes

The incorporation of moderate amounts of Ni(II), Co(II), Fe(II/III), and Mn(II/III) into aluminophosphate zeotype AlPO4-34 and Fe(II/III) into aluminophosphate zeotype AlPO4-36 was studied by broadline 31P NMR. The technique provided direct evidence on isomorphous substitution of framework aluminum by transition metals and allowed us to determine the extent of the substitution. 31P NMR proved to be complementary to other spectroscopic techniques such as X-ray absorption spectroscopy (XAS), M?ssbauer, electron paramagnetic resonance (EPR), and electron nuclear double resonance (ENDOR) spectroscopies. The position of the NMR signal belonging to phosphorus in the P(OAl)3(OMe) environment depended mostly on the magnitude of the hyperfine interaction between a phosphorus nucleus and an unpaired electron, which was delocalized from the transition metal atom Me by covalent bonding. The width of the NMR signal was dominated by dipolar coupling among phosphorus nuclei and nearest paramagnetic centers. In addition, broadline NMR of ethylenediamine-templated manganese phosphate (C2H10N2)[Mn2(HPO4)3(H2O)], which was used as a model compound, showed that on the basis of line positions and line widths different 31P signals could easily be assigned to different phosphorus crystallographic sites. The technique could thus be applied to extract valuable structural information about metal phosphates as well.     

Synthese de substances macromoleculaires renfermant des motifs monomeres derives de colorants—XVIII: Synthese d'oligoamides colores par structure

Oligoamides with amino end-groups have been reacted with acid chlorides of azo or quinophthalic dyes. Oligoamides with 4-nitro phenyl end-groups have been reduced to oligoamides with aminophenyl end-groups; they have been diazotized and coupled with β naphthol. Due to their low thermal stability, oligoamides containing azo groups cannot be spun; on the other hand, oligoamides with quinophthalic groups can be used as macromolecular dyes for polyamides. Coloured fibres have excellent mechanical properties and the dye cannot be extracted by solvent.     

Growth and production of buckwheat (Fagopyrum esculentum) treated with reduced, ambient, and enhanced UV-B radiation

The effect of enhanced UV-B radiation on buckwheat (Fagopyrum esculentum Moench. variety 'Darja'), an important high elevation crop, was studied in order to estimate its vulnerability in changing UV-B environment. Plants were grown in outdoor experiments from July to October under reduced and ambient UV-B levels, and an UV-B level simulating 17% ozone depletion in Ljubljana. During the development the following parameters were monitored: light saturated photosynthetic activity, transpiration, potential and effective photochemical efficiencies of photosystem II, the contents of photosynthetic pigments and methanol soluble UV-B absorbing compounds. At the end of the experiment, growth rate and production of seeds were estimated. In the following growth season the seeds collected from plants exposed to different UV-B treatments were tested for germination capacity. Total UV-B absorbing compounds during plant development were increased by UV-B radiation, photosynthetic pigments (chlorophyll a and b and carotenoids) decreased. Photosynthetic rate was lowered in an early stage of development. UV-B treatment resulted in the increase in the transpiration rate and consequently the decrease in water use efficiency (WUE). The disturbances in water economy and in photosynthesis affected the reproduction potential negatively; the production of seeds in plants cultivated under ambient and enhanced UV-B was 57 and 39% of the production of specimens treated with reduced UV-B, respectively. The germination of seeds collected from treated plants revealed on average about 95% success, independently of the treatment, but the time needed for germination was the shortest for seeds developed under enhanced UV-B level treatment. Enhanced UV-B radiation affected water relations and production of buckwheat, but not the potential of seeds for germination.     

Uncertainty in quantitative thin-layer chromatography

Globalization forces analysts to demand extended control of variability in analytical measurements. A calculation procedure named the "error budget model" following recommendations proposed more than 20 years ago by the Bureau International des Poids et Mesures is established as a rule for evaluating and expressing the measurement uncertainty across a broad spectrum of measurements. This metrological approach common in physical measurement is not applicable in separation techniques and cannot quantitate measurement uncertainty. Our experiments show that it can be used as a planning tool in the validation of thin-layer chromatographic (TLC) methods. A computer program that quantitates uncertainty components associated with potential sources of uncertainty in quantitative TLC is prepared and tested with experimental data. TLC plates with different qualities of stationary phases (TLC and high-performance TLC) spotted with different types of samples are measured. Application is performed manually and automatically. Plates are scanned with UV-vis scanners and a video documentation system in remission and transmission mode and fluorescence. Although the calculated values are close to the values obtained with validation procedures, the error budget approach cannot substitute validation. Calculated results can predict critical points in real quantitative TLC, but they cannot confirm the validity of a selected chromatographic procedure.     

Comparison of TLC and Spectrophotometric Methods for Evaluation of the Antioxidant Activity of Grape and Berry Anthocyanins

JPC – Journal of Planar Chromatography – Modern TLC - Variation of antioxidant activity was measured for differently prepared extracts of pressed residues (marc) from red wine making...     

Electron Paramagnetic Resonance Gives Evidence for the Presence of Type 1 Gonadotropin-Releasing Hormone Receptor (GnRH-R) in Subdomains of Lipid Rafts

This study investigated the effect of type 1 gonadotropin releasing hormone receptor (GnRH-R) localization within lipid rafts on the properties of plasma membrane (PM) nanodomain structure. Confocal microscopy revealed colocalization of PM-localized GnRH-R with GM₁-enriched raft-like PM subdomains. Electron paramagnetic resonance spectroscopy (EPR) of a membrane-partitioned spin probe was then used to study PM fluidity of immortalized pituitary gonadotrope cell line αT3-1 and HEK-293 cells stably expressing GnRH-R and compared it with their corresponding controls (αT4 and HEK-293 cells). Computer-assisted interpretation of EPR spectra revealed three modes of spin probe movement reflecting the properties of three types of PM nanodomains. Domains with an intermediate order parameter (domain 2) were the most affected by the presence of the GnRH-Rs, which increased PM ordering (order parameter (S)) and rotational mobility of PM lipids (decreased rotational correlation time (τc)). Depletion of cholesterol by methyl-β-cyclodextrin (methyl-β-CD) inhibited agonist-induced GnRH-R internalization and intracellular Ca²⁺ activity and resulted in an overall reduction in PM order; an observation further supported by molecular dynamics (MD) simulations of model membrane systems. This study provides evidence that GnRH-R PM localization may be related to a subdomain of lipid rafts that has lower PM ordering, suggesting lateral heterogeneity within lipid raft domains.     

Attractive surface force in the presence of dissolved gas: a molecular approach

Despite widespread evidence of the influence of dissolved air on hydrophobic interaction, the mechanisms of observed effects are still unknown. Although some experiments indicate that adsorbed gases can modify the structure of water next to hydrophobic surfaces, gas effects on measured forces have been observed only at large surface separations. Gas-specific depletion of water at a hydrophobic surface has been detected but was not reproduced in subsequent measurements. We use computer simulations to study short-ranged hydrophobic attraction in the absence and presence of dissolved gas and monitor gas adsorption at molecular resolution inaccessible in experiments. Although we observe a significant accumulation of dissolved gases at hydrophobic surfaces, even in supersaturated gas solutions surface concentrations remain too low to induce any significant change in the local structure of water and short-range surface forces. We present direct calculations of the hydrophobic force between model hydrocarbon plates at separations between 1.5 and 4 nm. Although stronger, the calculated solvation force has a similar decay rate as deduced from recent surface force apparatus measurements at a somewhat lower contact angle. Within the statistical uncertainty, short-range attraction is not affected by the presence of dissolved nitrogen, even in supersaturated solution with a gas fugacity as high as 30 atm. Comparisons of the adsorption behavior of N2, O2, CO2, and Ar reveal similar features in contrast to the peculiar suppression of water depletion reported for an Ar solution in a neutron reflectivity experiment. Our calculations reveal a notable difference between pathways to the capillary evaporation of pure water and gas-phase nucleation in confined supersaturated gas solutions.     

Etude théorique du spectre infra-rouge des complexes liés par liaison hydrogène à l'état gazeux: complexe ClH … O(CH3)2, son homologue deutérié et complexes voisins

Un modèle théorique est proposé en vue de reconstituer des spectres d'absorption IR des complexes du type ClH … O(CH₃)₂ en phase gazeuse. Ces complexes sont assimilés à des supermolécules triatomiques linéaires AH … B pour lesquelles la vibration v _AH et la vibration v _AH … B sont couplées par un potentiel anharmonique. Le terme couplant ces deux vibrations peut être atteint de manière précise par la connaissance de l'évolution du spectre en fonction de la température. Le modèle permet de reproduire de façon satisfaisante les spectres I.R. de ClH … O(CH₃)₂ et de ClD … O(CH₃)₂. On reproduit également mais de façon moins précise les spectres de quelques complexes voisins pour lesquels on ne possède pas de résultats en fonction de la température.     

Oxygen plasma functionalization of poly(p-phenilene sulphide)

Surface effects during plasma activation of poly(p-phenilene sulphide)—PPS have been studied. Samples that were exposed to weakly ionized highly dissociated oxygen plasma created an inductively coupled radiofrequency discharge with the power of 100 W. The electron density and temperature were measured with a double Langmuir probe and were 4 × 10¹⁵ m⁻³ and 3 eV, respectively, while the neutral atom density was measured with a fiber optics catalytic probe and was 4 × 10²¹ m⁻³. The surface tension was determined by measuring the contact angle of deionized water, while the appearance of surface functional groups was detected by XPS. The surface tension of untreated PPS was 7 × 10⁻³ N/m or/and increased to 7 × 10⁻² N/m in few seconds of plasma treatment. It remained fairly constant for longer plasma treatments. The XPS survey spectrum showed little oxygen on untreated samples, but its concentration increased to about 20 at.% in few seconds. Detailed high resolution XPS C 1s peak showed that the carbon was left fairly stable during plasma treatment. The main functional groups formed were rather sulphate in sulphite groups, as determined from high resolution S 2p peak. Namely, a strong transition from sulphide to sulphate state of sulfur was observed. The spontaneous deactivation of the polymer surface was measured as well. The deactivation was fairly logarithmic with the characteristic decay time of several hours.