Microextraction by packed sorbent optimized by statistical design of experiment as an approach to increase the sensitivity and selectivity of HPLC-UV determination of parabens in cosmetics.

A new approach to the quantitative analysis of parabens (PBs) in cosmetics, based on microextraction by packed sorbent (MEPS) followed by HPLC-UV detection is proposed. The development of optimal conditions for the sample preparation step was carried out in two stages. The potentially important factors that could influence the extraction were screened using the Plackett-Burman design approach, as a result of which, three statistically significant factors were selected from the nine studied. Thereafter, the selected variables were optimized by response surface methodology using a Central Composite Design. Under optimal conditions, the linear ranges for PBs analysis in cosmetic samples were 0.05-4 µg/mL with excellent precision. Limits of detection (LOD) of PBs in cosmetic samples were 2-5 ng/mL, and the extraction recovery ranged from 89 to 105 %. By comparing the chromatograms of the diluted shampoo sample before and after MEPS, the benefits of developed approach were shown. Then it was applied to the analysis of PBs in commercial hair cosmetic products: parabens were determined in all samples in which they were indicated on the package and in 1 of 12 samples labeled "paraben-free". Finally, the proposed method was compared with other analytical HPLC-UV methods with various sample pretreatment techniques for PBs analysis in cosmetics described in recent articles. Its sensitivity turned out to be one of the highest, while it is express, automated, meets the principles of green chemistry.

Isomeric derivatives of triazoles as new toxic decomposition products of 1,1-dimethylhydrazine.

Unsymmetrical dimethylhydrazine (UDMH) is a rocket propellant for carrier rockets and missiles. UDMH is environmentally hostile compound, which easily forms a variety of toxic products of oxidative transformation. The liquidation of unused UDMH from retired launch sites is performed by the complete burning of UDMH-containing wastes. Due cyclicity of the burning equipment the UDMH-containing wastes are subject of prolonged storage in contact with atmospheric oxygen and thus contains a complicated mixture of UDMH degradation products. High performance liquid chromatography (HPLC), high resolution mass spectrometry (HRMS) and NMR were used for the isolation on characterization of new highly polar and potentially toxic UDMH transformation products in the mixture. Two series of unreported isomers with high ionization cross section in electrospray ionization were isolated by repeated preparative HPLC. The structures of the isomers were established by tandem HRMS and NMR. The cytotoxicity of the isolated compounds has been preliminarily studied and found to be similar to UDMH or higher.