Solid-phase extraction of 4(5)-methylimidazole (4MeI) and 2-acetyl-4(5)-(1,2,3,4-tetrahydroxybutyl)-imidazole (THI) from foods and beverages with subsequent liquid chromatographic-electrospray mass spectrometric quantification

A method for the simultaneous determination of 4(5)-methylimidazole (4MeI) and 2-acetyl-4(5)-(1,2,3,4-tetrahydroxybutyl)-imidazole (THI) was developed using SPE and HPLC/MS. Solid-phase extraction using SCX Disc cartridges was used for isolation of the analytes from liquid samples. The lower LOQwas 0.1 ng/mL for 4MeI and 0.2 ng/ mL for THI. The linearity of the calibration curves was satisfactory as indicated by correlation coefficients >0.999. The CV for the intra- and inter-day precision was <5% (n = 6); the accuracy was in the range 98-103%. The recovery was > or = 97 and > or = 98% for THI and 4MeI, respectively. The method was used to determine THI and 4MeI in beverages, coffee, caramel colours and other samples.     

Computer Study of the Association Behavior of Gradient Copolymers: Analysis of Simulation Results Based on a New Algorithm for Recognition and Classification of Aggregates

We present a computer study of the association behavior of copolymer chains with a gradient part and soluble tail of variable length. As a simulation method we use dynamic Monte Carlo simulation on a simple cubic lattice with pair interaction parameters. The solvent quality and selectivity is modeled by the variation of pair interaction parameters between nearest neighbors on the lattice. The role of the length of soluble part in the self‐assembly and its effect on the structure of aggregates was the main goal of this work. The size and structure of aggregates were analyzed using an improved topological classification method which has been developed and tested in the present study. The structure and association numbers of aggregates were compared with those of linear diblock copolymers.

     

Interference-free determination of thallium in aqua regia leaches from rocks, soils and sediments by D(2)-ETAAS method using mixed palladium-citric acid-lithium chemical modifier

The mixture of palladium (chloride) with citric acid and lithium is proposed as a new chemical modifier for the elimination of interference occurred during the determination of Tl in aqua regia extracts from rocks, soils and sediments by electrothermal atomic absorption spectrometry using instrumentation with deuterium-lamp background correction (D₂-ETAAS). Palladium was preferred to rhodium and platinum as to analyte stabilization, citric acid served as an effective reducing agent facilitating formation of Pd-Tl stable covalent bonds playing an important role in the analyte stabilization. Citric acid in addition helps to remove most of interfering chloride at low temperature. The further addition of Li increased significantly the robustness of chemical modifier against strongly interfering ZnCl₂ matrix by binding free chlorine into a more stable LiCl molecule. In the presence of the proposed chemical modifier the temperature for the final step of pyrolysis was adjustable up to 1000 °C, without any noticeable loss of volatile Tl species and the interference of the rest chloride matrix was significantly reduced. The application of the modifier to direct determination of Tl in aqua regia extracts from rocks, soils and sediments has ensured the characteristic mass and LOD value for the original sample 13 pg and 0.043 μg g⁻¹, respectively (10-μL aliquots of sample) and has enabled the use of matrix-free standard solutions for attaining accurate analysis. The accuracy was verified by the analysis of certified reference samples and by the comparison of results with those found by an inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometer (ICP-oa-TOFMS) method.     

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry of monoterpenoids as a powerful tool for grape origin traceability

The establishment of the monoterpenoid profile of Vitis vinifera L. cv. 'Fern?o-Pires' white grape was achieved by headspace solid-phase microextraction coupled with comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToF-MS). The plot of the first dimension versus the second dimension retention times using the m/z 93, 121, and 136 was used. The grapes were found to contain 56 monoterpenoids identified by GCxGC-ToF-MS. From these, 20 were reported for the first time in grapes. According to their chemical structure, the compounds were organized in different groups: monoterpene hydrocarbons and monoterpene oxygen-containing compounds, this later divided in oxides, alcohols (monoterpenols and monoterpendiols), aldehydes, esters, and ketones. A database composed by the retention indices of monoterpenoids calculated in the bi-dimensional column set was created, representing a developmental step in monoterpenoid analysis using a GCxGC system. Remarkable results were also obtained in terms of compound classification based on the organized structure of the peaks of structurally related compounds in the GCxGC contour plot. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This study proposes a methodology and provides data that can be applied to determine the monoterpenoid profile of grapes, and its extension to the analysis of musts, and wines. As monoterpenoids are secondary metabolites whose synthesis is encoded by variety-related genes, the terpenoid profile may be used as a way to trace its varietal origin.     

Light absorption properties of the rabbit cornea repeatedly irradiated with UVB rays

Under normal conditions, the cornea absorbs the majority of UVB (ultraviolet B, 280-320 nm) rays, which is very important for the protection of the inner eye against their damaging effect. Our previous studies have shown that repeated irradiation of the rabbit cornea with UVB rays for 5 days (daily dose of 1.01 J cm(- 2)) caused photokeratitis accompanied by swelling (hydration) of the corneal stroma, thinning of the corneal epithelium and decrease in antioxidants. The purpose of this study was to examine the light absorption properties of such damaged rabbit cornea. Results of both spectrophotometry of the whole corneal buttons and corneal tissue dissolved in sodium hydroxide show that because of above mentioned disturbances, UVB-irradiated cornea absorbs more light throughout the whole measurable UV-VIS spectral range than the normal cornea. Increased corneal thickness (result of hydration), changes of corneal transparency (the cornea becomes grayish) and some increase in protein content all contribute to the increased light absorption of UVB irradiated corneas. We suggest that the UVB-irradiated cornea, although damaged and nearly without antioxidants, might actually through its higher UV absorbance protect the inner eye against further damage from UVB rays.     

Palladium-citric acid-ammonium fluoride as a matrix modifier for overcoming of interferences occurring during the direct determination of Sn in aqua regia extracts from environmental samples by D2-ETAAS

When tin is to be determined in such a complex matrix like aqua regia extracts of environmental samples by electrothermal atomic absorption spectrometry (ETAAS), spectral interferences occur when deuterium-lamp (D₂) background correction is used, even using high pyrolysis temperature of 1400 °C achieved with palladium with citric acid chemical modifier. We have found that the further addition of NH₄F to palladium with citric acid chemical modifier is essential for overcoming the above-mentioned problems for which aluminium oxide is most probably responsible. It is supposed, that NH₄F enables volatilization of the alumina matrix formed by hydrolysis from the chloride salt and interfering in a gas phase via the formation of AlF₃ which could be, in contrast to aluminium oxide, removed from the graphite furnace during the pyrolysis stage. Using the proposed chemical modifier, the direct and accurate determination of Sn in aqua regia extracts from rocks, soils and sediments is possible even when using matrix free standard solutions. This presumption was confirmed by the analysis of certified reference samples and by the comparison with inductively coupled plasma time of flight mass spectrometry (ICP-TOFMS) method. Characteristic mass and LOD value for the original sample (10-μL aliquots of sample) was 17 pg and 0.055 μg g⁻¹, respectively.     

Testing the structure of multistage stochastic programs

A fixed topology of stages and/or a fixed branching scheme are common assumptions for applications and numerical solution of scenario based multistage stochastic programs. Using contamination technique to test this structure, we extend the results of Dupačová (Contamination for multistage stochastic programs. In: Hušková M, Janžura M (eds) Prague stochastics. Matfyzpress, Praha, pp 91–101, 2006a) to stochastic programs with multistage polyhedral risk objectives. The ideas are exemplified by bond portfolio management problems and complemented by illustrative numerical results.     

Transferrin immunoextraction for determination of carbohydrate‐deficient transferrin in human serum by capillary zone electrophoresis

CZE‐based assays for carbohydrate‐deficient transferrin (CDT) in which serum is mixed with an Fe(III) ion‐containing solution prior to analysis are effective approaches for the determination of CDT in patient samples. Sera of patients with progressed diseases, however, are prone to interferences comigrating with transferrin (Tf) that prevent the proper determination of CDT by CZE in these samples. The need of a simple and economic approach to immunoextract Tf from human serum prompted us to investigate the use of a laboratory‐made anti‐Tf spin column containing polyclonal rabbit anti‐human Tf antibodies linked to Sepharose 4 Fast Flow beads. This article reports extraction column manufacturing and column characterization with sera having normal and elevated CDT levels. The developed procedure was applied to a number of relevant hepatology and dialysis patient samples and could thereby be shown to represent an effective method for extraction and concentration of all Tf isoforms. Furthermore, lipemic sera were delipidated using a mixture of diisopropyl ether and butanol prior to immunoextraction. CDT could unambiguously be determined in all pretreated samples.     

Crop planning optimization model: the validation and verification processes

Each optimization problem in the area of natural resources claims for a specific validation and verification (V&V) procedures which, for overwhelming majority of the models, have not been developed so far. In this paper we develop V&V procedures for the crop planning optimization models in agriculture when the randomness of harvests is considered and complex crop rotation restrictions must hold. We list the criteria for developing V&V processes in this particular case, discuss the restrictions given by the data availability and suggest the V&V procedures. To show its relevance, they are applied to recently constructed stochastic programming model aiming to serve as a decision support tool for crop plan optimization in South Moravian farm. We find that the model is verified and valid and if applied in practice—it thus offers a plausible alternative to standard decision making routine on farms which often leads to breaking the crop rotation rules.     

Study of the Ternary Systems M (II)(NO3)2–LiNO3–H2O ( M (II)?5?Mg, Ca, Sr, Ba) at 25°C

 The isothermal solubility diagrams of four aqueous systems containing lithium nitrate and nitrates of group IIA metals – magnesium, calcium, strontium, and barium – were studied at 25°C. No double salt formation was observed. The results were compared with similar nitrate and chloride systems. Some trends in the shape of the phase diagrams were observed. Hydration analysis was applied to the solubility branches, rendering information about ionic processes in saturated solutions. Further, the ratio of activity coefficients of the saturating solid phase in ternary and binary solutions (γ/γ₀) was obtained.