Evaluation of ammonium fluoride for quantitative microwave-assisted extraction of silicon and boron from different solid samples

A novel, simple, efficient and environmentally friendly closed-microwave-assisted extraction (MAE) method of silicon and boron from a variety of industrial and environmental samples using ammonium fluoride as an extractant was developed. This method avoids handling the corrosive and toxic HF and prevents the potential risk of analyte loss due to the creation of volatile SiF₄ and BF₃ in the presence of HF. Atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry were employed for the subsequent analysis of the resulting supernatant for determination of Si and B, respectively. Certified reference material BCR^®-032 Natural Moroccan Phosphate Rock (phosphate fertiliser) was taken to optimise the extraction parameters such as the sample amount, extraction temperature and time and the volume of the extractant. The optimum extraction parameters evaluated using a fractional factorial design were as follows: 50 mg of the sample extracted with 5 mL of 100 g L^?1 NH₄ F for 15 min at 180°C. The optimised MAE procedure was successfully applied to nine different matrix reference materials intended primarily for validation of methods for determination of components in fertilisers, sludge, plants and fly ash. The obtained results were in a good agreement with the certified or comparative values with an overall precision better than 10% in all cases. The proposed method is recommended for fast and reliable preparation of samples with silicon content <8.2% (w/w). However, further decreasing the sample mass to 10 mg enabled the quantitative extraction of silicon from fly ashes at levels of 23% (w/w).     

An improved in vivo deuterium labeling method for measuring the biosynthetic rate of cytokinins

An improved method for determining the relative biosynthetic rate of isoprenoid cytokinins has been developed. A set of 11 relevant isoprenoid cytokinins, including zeatin isomers, was separated by ultra performance liquid chromatography in less than 6 min. The iP-type cytokinins were observed to give rise to a previously-unknown fragment at m/z 69; we suggest that the diagnostic (204-69) transition can be used to monitor the biosynthetic rate of isopentenyladenine. Furthermore, we found that by treating the cytokinin nucleotides with alkaline phosphatase prior to analysis, the sensitivity of the detection process could be increased. In addition, derivatization (propionylation) improved the ESI-MS response by increasing the analytes' hydrophobicity. Indeed, the ESI-MS response of propionylated isopentenyladenosine was about 34% higher than that of its underivatized counterpart. Moreover, the response of the derivatized zeatin ribosides was about 75% higher than that of underivatized zeatin ribosides. Finally, we created a web-based calculator (IZOTOP) that facilitates MS/MS data processing and offer it freely to the research community.     

Zirconia—A stationary phase capable of the separation of polar markers of myocardial metabolism in hydrophilic interaction chromatography

Creatine, phosphocreatine, and adenine nucleotides are highly polar markers of myocardial metabolism that are poorly retained on RP silica sorbents. Zirconia represents an alternative material to silica with high promise to be used in hydrophilic interaction chromatography (HILIC). This study describes a first systematic investigation of the ability of ZrO₂ to separate creatine, phosphocreatine, adenosine 5′‐monophosphate, adenosine 5′‐diphosphate, and adenosine 5′‐triphosphate and compares the results with those obtained on TiO₂. All analytes showed a HILIC‐like retention pattern when mobile phases of different strengths were tested. Stronger retention and better column performance were achieved in organic‐rich mobile phases as compared to aqueous conditions, where poor retention and insufficient column performance were observed. The effect of mobile phase pH and ionic strength was evaluated as well. The analysis of myocardial tissue demonstrated that all compounds were separated in a relevant biological material and thus proved ZrO₂ as a promising phase for HILIC of biological samples that deserves further investigation.     

The Phototoxic Potential of the Flavonoids,Taxifolin and Quercetin

Quercetin, one of the most abundant polyphenols in the plant kingdom has been shown to be photodegraded on exposure to UV light. Despite the fact, it is a component of several dermatological preparations. Its phototoxic potential has not been evaluated to date. The aim of this study was to assess whether photo‐induced degradation of quercetin is linked to phototoxic effects on living cells. Its dihydro derivative, taxifolin, was included in the study. For evaluation, the 3T3 Neutral Red Uptake Phototoxicity Test according to OECD TG 432 was used. To better approximate human skin, HaCaT keratinocytes, normal human epidermal keratinocytes and dermal fibroblasts were used, apart from the Balb/c 3T3 cell line. Quercetin showed a dose‐dependent photodegradation in aqueous and organic environments and a phototoxic effect on all used cells. Quercetin pretreatment and following UVA exposure resulted in increased reactive oxygen species production and intracellular glutathione level depletion in human dermal fibroblasts. Taxifolin was found completely nonphototoxic and photostable. As only in vitro methodology was used, further studies using 3D skin models and/or human volunteers are needed to confirm whether exposure to sunlight, tanning sunbeds and/or phototherapy in people using cosmetics containing quercetin is a health risk.     

The mechanism of the electrochemical oxidation of thiourea

Cyclic voltammetry and potentiostatic coulometry were used to study the electrochemical oxidation of thiourea in aqueous solutions of nitric acid, nitric acid—ammonium nitrate, and ammonium nitrate—ammonium hydroxide and in acetonitrile. These studies were carried out at glassy carbon and/or platinum working electrodes. In acetonitrile, the cyclic voltammograms show one oxidation peak at + 0.6 V and a reduction peak at —0.1 V. In aqueous solutions up to about pH 6, there is a second oxidation peak at 1.3 V which is irreversible and its height is sensitive to acidity. These experiments have confirmed that in acidic and neutral solutions the oxidation of thiourea proceeds via a slow 1-e transfer reaction producing a radical [(NH₂)₂—C—S]⁺. Further direct oxidation of this radical takes place only at higher potentials (ca. 1.2 V) and involves hydration and protontransfer equilibria. Otherwise, C,C'-dithiodiformamidinium ion is formed by a fast dimerization reaction. Coulometric and chronopotentiometric measurements have shown that in strong acid the second oxidation step involves one electron, while at lower acidities the further oxidation involving three (and possibly five) electrons proceeds in two (or three) steps of very similar potential.     

Application of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry in human metabolomic studies

In this paper several characteristic features of time-of-flight mass spectrometry in coupling with gas chromatography are demonstrated and the parameters are compared to quadrupole mass analyzer. In the second part, the comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry was applied in human metabolomic field, particularly in the determination of pathological markers of Inherited Metabolic Disorders (IMDs).     

Control variational method approach to bending and contact problems for Gao beam

This paper deals with a nonlinear beam model which was published by D.Y.Gao in 1996. It is considered either pure bending or a unilateral contact with elastic foundation, where the normal compliance condition is employed. Under additional assumptions on data, higher regularity of solution is proved. It enables us to transform the problem into a control variational problem. For basic types of boundary conditions, suitable transformations of the problem are derived. The control variational problem contains a simple linear state problem and it is solved by the conditioned gradient method. Illustrative numerical examples are introduced in order to compare the Gao beam with the classical Euler-Bernoulli beam.     

Reactivity in radical polymerisation: An improved method for the prediction of monomer reactivity ratios and transfer constants

Half a century after the Q-e scheme was promulgated, a substantially improved method for predicting monomer reactivity ratios and transfer constants has been developed from the Patterns of Reactivity scheme. It is based on the same premise as its predecessors, that reactivity is controlled partly by thermodynamic and partly by polar factors, but the new treatment yields values much closer, on average, to the reported experimental data.