Sensitive capillary electrophoretic determination of mercury species with amperometric detection at a copper electrode after cation exchange preconcentration

A capillary electrophoretic method for the separation of four mercury species with amperometric detection was developed. Inorganic Hg2+, methyl-, ethyl-, and phenyl-mercury were complexed with L-cysteine and separated in a counterelectroosmotic mode in an electrolyte solution comprised of 20 mM sodium tetraborate at pH 9.5. Amperometric detection of separated species was achieved at passivated copper electrode under electrocatalytic oxidation conditions. The four mercury species were separated in less than 8 min with LODs ranging from 170 to 450 microg/L. Cation exchange preconcentration was used to decrease the LODs down to 1.7 microg/L.     

First Total Syntheses of Novel Non-Enzymatic Polyunsaturated Fatty Acid Metabolites and Their Identification in Edible Oils

Oxidative stress (OS) is an in vivo process leading to free radical overproduction, which triggers polyunsaturated fatty acid (PUFA) peroxidation resulting in the formation of racemic non-enzymatic oxygenated metabolites. As potential biomarkers of OS, their in vivo quantification is of great interest. However, since a large number of isomeric metabolites is formed in parallel, their quantification remains difficult without primary standards. Three new PUFA-metabolites, namely 18-F_3t-isoprostane (IsoP) from eicosapentaenoic acid (EPA), 20-F_4t-neuroprostane (NeuroP) from docosahexaenoic acid (DHA) and 20-F_3t-NeuroP from docosapentaenoic acid (DPA_n-3) were synthesized by two complementary synthetic strategies. The first one relied on a racemic approach to 18(RS)-18-F_3t-IsoP using an oxidative radical anion cyclization as a key step, whereas the second used an enzymatic deracemization of a bicyclo[3.3.0]octene intermediate obtained from cyclooctadiene to pursue an asymmetric synthesis. The synthesized metabolites were applied in targeted lipidomics to prove lipid peroxidation in edible oils of commercial nutraceuticals.     

Ion exchange preconcentration and separation of mercury species by CE with indirect contactless conductometric detection

Capillary electrophoretic separation of four mercury species (inorganic Hg(2+), methyl-, ethyl-, and phenylmercury) was achieved in less than 8 min with an electrolyte consisting of 150 mM 2-amino-2-methyl-propanol (AMP) at pH 11.6. The analytes were complexed with 0.1% mercaptopropionic acid (MPA), separated in counter-EOF as anionic complexes, and detected by a contactless conductometric detector. Ion exchange preconcentration with on-column formation of MPA-mercury complexes was developed. Preconcentration factors of 25-150 were achieved and LODs in the range of 2.9-6.9 ng/mL were feasible. This method may prove to be applicable as a rapid screening method for mercury speciation in environmental samples.     

Comparison of solid-phase and single-drop microextractions for headspace analysis of herbal essential oils

The analytical microextraction methods of gas chromatography coupled with flame ionisation detector (GC-FID) for determination of selected essential oils in herbs were proposed. Two microextraction methods for the isolation of essential oils from plants such as Lavandula spica L., Melissa officinalis L., Mentha piperita L. and Salvia officinalis L. were used. The methods of solid-phase and single-drop microextractions, were optimised and compared. The obtained LOD values for all studied essential oils were found to be within 2.5–20.5 μg for SDME and 57.0–139.8 μg for SPME method per 100 g of dried sample leaves. The appropriate LOQ values were then 8.4–68.4 μg for SDME and 189.8–466.1 μg for SPME of target analytes per 100 g of dried sample leaves.      

Corrosion of titanium diboride in molten FLiNaK(eut)

Pure and enriched titanium dibromide (TiB₂) samples (prepared by hot isostatic pressing) with different mole ratios of Ni and Ta were investigated in contact with molten eutectic salt (FLiNaK_(eut); LiF/NaF/KF 42.5 mole %: 11.5 mole %: 42.0 mole %) at 600°C. Corrosion resistance of the materials was studied, the mass losses and depths of corrosion were calculated, and sample surfaces were investigated by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX). Nickel addition decreased the corrosion resistance of TiB₂. Simultaneous additions of both elements, Ni and Ta, as well as the addition of Ta only showed reducing effect on grain formation and they increased the corrosion resistance which is highest in the last case.     

Interactions of 2,5- and 3,5-dimethylphenols with co-exchanged montmorillonite

The influence of different steric and electronic properties of 2,5- and 3,5-dimethylphenols (2,5 and 3,5-DMP) on the type of interactions with Cobalt-exchanged montmorillonite (Co-MMT) was studied. The results of X-ray diffraction (XRD), IR-spectroscopy and thermal (TG, DTG) analysis show that phenol derivatives are intercalated into the interlayer space of montmorillonite. Thermal decomposition in the temperature interval 20–700 °C of Co-MMT with 3,5-DMP proceeds in four steps while Co-MMT with 2,5-DMP decompose only in three steps. These differences are connected with different acid–base interactions of individual phenol derivatives in the interlayer space of montmorillonite, which is in agreement with the results of IR-spectroscopy.     

Online molecularly imprinted solid‐phase extraction coupled to liquid chromatography‐tandem mass spectrometry for the determination of hormones in water and sediment samples

The molecularly imprinted SPE directly coupled to RP LC‐MS/MS method has been developed and successfully validated for the determination of six hormones in water and sediment samples. The method is based on the use the home‐made column filled with a molecularly imprinted sorbent (imprinted against estrogens) that was used under nonaqueous conditions. Thus, its high selectivity could be utilized resulting in low matrix components’ coextraction. The method showed excellent recovery (92–105%) and satisfactory sensitivity (LOQs water: 1.9–4.0 ng/L; LOQs sediment: 0.2–0.5 ng/g). The intra‐ and interprecision for water and sediment was in the range of 4.0–6.0% and 4.4–7.6%, respectively. Finally, 20 water and sediment samples collected from the Svratka river were analyzed. Only estrone was quantified in eight water samples (4.4–7.1 ng/L); no analytes were found in sediment samples.     

Effect of addition of ameliorative materials on the distribution of As,Cd, Pb,and Zn in extractable soil fractions

The effects of lime, limestone, and zeolite addition on the availability of As, Cd, Pb, and Zn in three contaminated soils were investigated in a pot experiment after four vegetation periods of spring wheat, spring barley, and oat. The results showed different responses of extractable element portions to soil amendment when 0.01 mol dm⁻³ aqueous CaCl₂ was applied as a soil extraction agent. Substantial differences were evident among the investigated elements as well as among the individual soil treatments. Except natural zeolite, the ability of ameliorative materials to redistribute cadmium and zinc from a soil solution into less mobile but labile soil fractions was observed. The lead availability was less affected and the extractability of arsenic even increased in some of the treated pots. Moreover, the availability of arsenic was more affected by different characteristics of experimental soils than by individual soil treatments. It was found that these treatments can be applied neither for multicontaminated nor for all the soil types. The soil treatments had a lower effect on the less mobile soil fractions. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Application of Contactless Impedance Detection to Determination of Substances in Gaseous Phase

A simple cell, consisting of two insulated wire electrodes placed in a PTFE tube through which the test gaseous phase flows, has been applied to capacitively coupled contactless conductometric detection (C⁴D) and determination of water vapour in the air, to examine the possibilities of the use of C⁴D for analyses of gaseous samples. It has been found that the measurement is sufficiently sensitive and reliable for determinations of common concentrations of water in the air. The dynamic characteristics and the signal stability demonstrate that the cell will be suitable for long‐term continuous monitoring of the air humidity. Qualitative tests indicate that vapours of organic solvents can also be monitored. To the authors knowledge, this is the first attempt to use C⁴D in gas analyses.     

Water Vapor Adsorption in Porous Building Materials: Experimental Measurement and Theoretical Analysis

An experimental and theoretical analysis of the water vapor adsorption in several types of porous building materials is presented. For the measurement of adsorption isotherms, a DVS-Advantage water sorption device is used. The experimental data is analyzed using theoretical formulas based on the BET, BSB, BDDT, and FHH isotherms, assuming a mono as well as multi-layer water vapor adsorption. The BSB equation is found to provide a good approximation for the relative humidities below 0.6–0.7, whereas the FHH equation shows a sufficient accuracy for the relative humidities above 0.4–0.5. Based on a combination of BSB and FHH isotherms, a semi-empirical formula is proposed that allows one to obtain a very accurate approximation of experimental data for all analyzed materials and all values of the relative humidity.