Carrier gas as a new factor influencing the selectivity of the gas-stationary liquid phase chromatographic system

This paper generalizes studies on the influence of carrier gas on relative and absolute retention values. This line of research is also of importance due to the fact that, in the opinion of many chromatographers, the role of the carrier gas is limited only to transporting analyzed compounds along the column. However, even under conditions of the conventional capillary gas-liquid chromatography (i.e. at column pressures under 5 atm) carrier gas (its nature and pressure) significantly influences retention and separation of the analyzed compounds. First, carrier gas (N2 and CO2, for example) dramatically affects relative retention values. For this reason, one should use limit values of alpha(ij) (0) = lim alpha(ij)(P(av)) and I(i)(0) = lim Ii(Pav) I(0) = limI(i) (Pav) with Pav-->0 as chromatographic constants, rather than traditional relative retention values alpha(ij)(P(av)) and I(i)(P(av)). Second, the average pressure Pav of the carrier gas in a column and the nature of the carrier gas influence the selectivity of the gas-stationary liquid phase chromatographic system. Third, wishing to maximize the role of the carrier gas as a factor that improves separation of analyzed compounds, we should design a special gas chromatograph that would allow work with pressures in the column up to 30-50 atm.     

A pH-controllable electrochemical molecule switch employing a new electrochemical measurement system as switching transducer

A new design concept of electrochemical pH-controllable molecular switch is presented by utilizing a new electrochemical measurement system as switching transducer. A pH sensor is connected in series between the terminal points of the working and counters electrodes of a potentisostat, and immersed in the solution together with a reference electrode, establishing a novel electrochemical measurement system. In this system, the variation of pH-controllable interface potential at the pH-sensing film/solution interface can be converted to current response when amperometry technique is employed. Based on this unique current–potential relationship, a pH-controllable switch is designed to monitor the protonation and deprotonation reaction of pH-sensing molecule. The current direction interchanges between positive and negative via pH control, illustrating a reversible conformation transition between protonated state and deprotionated state of molecule. The magnitude of current value represents the degree of protonation and deprotonation reaction of molecule. The strategy is successfully demonstrated with a remarkably reversible polyaniline-based pH-controllable switch, which confirms the feasibility of the novel electrochemical measurement system as switching transducer for designing electrochemical pH-controllable switches. This study may open up a potential avenue to construct the electrochemical pH-controllable switches.     

Stability results on a chemical system

In this paper, we first use the small gain theorem to present some sufficient conditions for global asymptotic stability of an equilibrium point of the bromate-malonic acid-ferroin system. Then we give an estimate of ultimate bounded set of this system.     

International comparability of chemical measurement results

The international system of units (SI) is an internationally recognized system based on standards of long-term stability; by the use traceable measurements it provides an international infrastructure for realizing comparable measurements. The work of the Consultative Committee for Amount of Substance (CCQM) and the implementation of the Mutual Recognition Arrangement (MRA) are facilitating an international programme for metrology in chemistry to extend this infrastructure to the field of chemical measurements. The major points of this programme, which include the execution of international comparisons and the construction of a key comparison and calibration database at the BIPM, are described.     

Immobilized urokinase column as part of a specific detection system for plasminogen species separated by high-performance affinity chromatography

Immobilized urokinase was used as part of a post-column reactor for the specific detection of human plasminogen species which were fractionated using a high-performance affinity column. After on-line activation of each peak, plasmin activity was measured by mixing the eluate with a specific fluorogenic substrate and the product was detected by a fluorescence monitor. This detection system gave linear calibration graphs for both purified plasminogens (0.1-50 micrograms) and plasminogens contained in plasma (25-100 microliters). Relative standard deviations for the determination of plasminogens in plasma were 6.1-6.6% (n = 12), showing good reproducibility. The detection limit was as low as 0.1 micrograms of plasminogen. Immobilized urokinase was very stable and no appreciable decrease in activity was found after 100 cycles of operation. In combination with an immobilized benzamidine column, this system made it possible to separate and detect Glu-plasminogen and Lys-plasminogen contained in human plasma samples as small as 100 microliters without any pretreatment.     

When is sampling part of the measurement process?

Accreditation and Quality Assurance -     

Human hair as a pollutant dosimeter

Human hair has been proved to be a better dosimeter than even blood for tracing most of the heavy metal toxins when they penetrate the biosphere. The high precision of the neutron activation analysis (NAA) enabled researchers to elegantly differentiate between endogenous and exogenous contamination and to thoroughly study poisonings caused by these physiologically-unimportant elements. An extensive amount of bench-scale work has been accomplished in these laboratories to show the capacity of INAA to detect the presence of 10 nuclides (or more) with a precision of about 5%. The principal objective of the present study was to employ this assaying power and the tendency of scalp hair to uptake metals from aqueous solutions, to design an adsorption system which can easily be used by the waste-management people who are searching for a cost-effective technique to monitor and remove these pollutants from relatively large volumes of industrial effluents.     

Validation of a new measuring system for water turbidity field measurements

Turbidity is an essential parameter for describing water quality by direct and indirect impacts on fish, invertebrates and aquatic plants. Currently, environmental monitoring measurements are carried out with appropriate quality by accredited testing laboratories, but there is also a need for employing the third sector, i.e. citizens and voluntaries in environmental monitoring. A device called “Secchi3000” was developed as a low-cost and simple-to-operate tool so that water quality measurements can also be carried out by non-experts and citizens. The measurement using the new device is simple: The user fills the container with water and places the measurement structure in the container. The user takes a photograph with the camera on a mobile phone through a hole in the lid. The software sends the photograph to a server, which analyses the photographs automatically. Finally, the results are returned to the user’s mobile phone and stored on a database for further analysis. In this study, the measuring system for turbidity measurements in natural waters was validated. Validation included an estimation of the limit of quantification, investigations of the influence of water colour and illumination conditions on turbidity measurement values and the estimation of measurement uncertainty. A comparison of turbidity results obtained with the new device and laboratory instrument in natural water samples was carried out, and turbidity values obtained with different mobile phones were compared. According to the validation results, the new device was appropriate for the measurement of turbidity lower than 7 FNU (Formazine Nephelometric Unit). An algorithm applied for present turbidity calculations is not fully suitable for higher turbidities. For potential routine use, this is not a major problem, since most Finnish natural waters have turbidities lower than 7 FNU. For official monitoring purposes, the limit of the quantification needs to be lower than presently achieved (1.7 FNU). Although the present configuration of the Secchi3000 device is not yet fully suitable for official environmental monitoring, it will already enable the involvement of the third sector in water quality monitoring, and in this way, citizens’ observations could then serve at least as supplementary information for reporting and surveys.     

Cholesterol surrogates incorporating a benzophenone as part of the sterol tetracycle

Photoactivatable analogues 4-6 of cholesterol (1), having their cross-linking site in the ring D sterol region, have been synthesized starting from bromotetralone 14 via enantioselective Robinson annulation to enone 13 and Suzuki carbonylative coupling to the appropriate phenylboronic acid. Each of 4-6 was shown to substitute successfully for 1 in an assay of apo A-I-induced cellular cholesterol efflux, indicating that these analogues equilibrated with 1 in all major cellular pools.     

Post column derivatization with a lead dioxide solid phase reactor as part of a continuous chromatographic detection system: Speciation measurements of chromium

Summary A post chromatographic chemical reaction detector is described for the determination of Cr (III) and Cr (VI) in the range of 100ng/ml to 10μg/ml. All chromium species which exist in a lower oxidation state than the sixvalent form are oxidized to chromate in a lead dioxide solid phase reactor. The detection is performed by complexation of the chromate with 1,5-diphenylcarbazide, which forms a red-violet complex detectable at 540 nm. The conditions which are necessary for a fast oxidation inside the solid phase reactor are discussed. The system which can also be run in the flow injection mode is applied to measurements of synthetic waste waters and to samples from a steel work. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Education and training of laboratory staff as a part of laboratory competence

Competence of laboratory staff is an important part of the technical competence of each laboratory. Because the speed at which knowledge goes out of date is increasing, maintaining laboratory staff competence at an appropriate level can be a very demanding requirement, especially for laboratories operating in a free market with little or no financial help from the state or from the larger organisation they possibly belong to. In order to manage staff competence effectively and efficiently, a laboratory must first define its services and the processes needed for realisation of these services. Responsibility for each step in these processes can then be assigned and gap analysis of current competence can be performed. This article analyses the requirements of ISO/IEC 17025 standard and gives some practical advice and solutions how to organize and manage staff competence.     

Oxoneptunium(v) as part of the framework of a polyoxometalate

(NH4)14Na4[(Np3W4O15)(H2O)3(BiW9O33)3].62H2O (1) and (NH4)14.5Na3.5[(Np3W4O15)(H2O)3(SbW9O33)3].40.5H2O (2) each contain three neptunyl(v) moieties encapsulated within heteropolyoxotungstate frameworks in which axial {NpO2}+ oxygens form one face of a WO6 octahedron.     

Crystallization kinetics of polypropylene with hyperbranched polyurethane acrylate being used as a toughening agent

The crystallization kinetics of polypropylene (PP) with hyperbranched polyurethane acrylate (HUA) being used as a toughening agent was studied by isothermal and nonisothermal differential scanning calorimetry (DSC). The presence of a small amount of HUA (2-7%) remarkably influences the crystallizability of PP. An addition of HUA leads to an increase in the number of effective nuclei, thus resulting in an increase of crystallization rate and a stronger trend of instantaneous three-dimensional growth. For isothermal crystallization, Avrami exponents were determined to be about 2.97 for pure PP and 3.51 for the HUA/PP blend containing 5% HUA (HUA-PP). The half crystallization time (t_1/2) of pure PP was measured to be 8.43 min, while being 3.28 min for HUA-PP at the crystallization temperature of 132 °C. The nonisothermal crystallization kinetics of HUA/PP blends was analyzed by Avrami, Ozawa and Kissinger methods. It has also been proved that an addition of HUA could increase the crystallization rate of PP. Moreover, the crystallization activation energies of pure PP and HUA-PP were estimated by Kissinger and Friedman methods.     

Thermogravimetry as a tool for measuring of fracturing fluid absorption in shales

A series of flame-retardant ethylene–vinyl acetate (EVA) composites with different contents of aluminum phosphate (AHP) and Trimer were prepared. The synergistic flame-retardant effects of the Trimer with AHP in EVA/AHP blends were studied by limiting oxygen index (LOI) tests, UL-94 tests, cone calorimeter tests, thermogravimetric analysis, and scanning electron microscopy (SEM). The LOI and UL-94 results showed that the system containing AHP and Trimer was very effective in improving the flame retardancy of EVA. When the mass ratio of AHP and Trimer was 3:1, the highest flame retardancy could be obtained, and when the flame-retardant loading was 30 wt%, the EVA/AHP/Trimer (7.5%) sample could achieve the V-0 rating in UL-94 tests, at the same time, its LOI value was 24.4%. The TG and DTG results showed that the addition of flame retardants catalyzes EVA decomposition in the first stage and generates a more stable char residue in the second stage. Consequently, an efficient reduction in the flammability parameters, such as heat release rate, total heat release, smoke production rate, and total smoke production could be observed. In addition, it was observed from the SEM observations of the morphological features that the AHP and Trimer combination, at the optimum proportion, could promote the formation of compact charred layers and prevent their cracking, which effectively protected the underlying materials from burning.     

Methodological factors influencing measurement and processing of plasma reelin in humans

Background

Reelin, intensively studied as an extracellular protein that regulates brain development, is also expressed in a variety of tissues and a circulating pool of reelin exists in adult mammals. Here we describe the methodological and biological foundation for carrying out and interpreting clinical studies of plasma reelin.

Results

Reelin in human plasma was sensitive to proteolysis, freeze-thawing and heating during long-term storage, sample preparation and electrophoresis. Reelin in plasma was a dimer under denaturing conditions. Boiling of samples resulted in laddering, suggesting that each of the 8 repeats expressed in reelin contains a heat-labile covalent bond susceptible to breakage. Urinary-type and tissue-type plasminogen activator converted reelin to a discrete 310 kDa fragment co-migrating with the major immunoreactive reelin fragment seen in plasma and also detected in brain. (In contrast, plasmin produced a spectrum of smaller unstable reelin fragments.) We examined archival plasma of 10 pairs of age-matched male individuals differing in repeat length of a CGG repeat polymorphism of the 5'-untranslated region of the reelin gene (both alleles < 11 repeats vs. one allele having >11 repeats). Reelin 310 kDa band content was lower in subjects having the long repeats in all 10 pairs, by 25% on average (p < 0.001). In contrast, no difference was noted for amyloid precursor protein.

Conclusions

Our studies indicate the need for caution in measuring reelin in archival blood samples, and suggest that assays of plasma reelin should take into account three dimensions that might vary independently: a) the total amount of reelin protein; b) the relative amounts of reelin vs. its proteolytic processing products; and c) the aggregation state of the native protein. Reelin-plasminogen activator interactions may affect their roles in synaptic plasticity. Our results also suggest that the human CGG repeat polymorphism affects reelin gene expression, and may affect susceptibility to human disease.