Study of Electrochemical Oxidation of Xanthohumol by Ultra-Performance Liquid Chromatography Coupled to High Resolution Tandem Mass Spectrometry and Ion Mobility Mass Spectrometry

Electrochemically assisted oxidation off-line combined with UPLC/ESI–MS and ion mobility mass spectrometry enabled us to gain insight into the oxidation mechanisms of xanthohumol. Several types of monomeric oxidation products were identified, i.e., monohydroxylated and dehydrogenated derivatives and related quinones. Besides, high contents of dimers were observed. The structures of four main oxidative condensation products of two xanthohumol molecules were proposed based on combination of retention time, exact mass measurement, fragmentation pattern, data from on-line ion mobility mass spectrometric experiments and with the support of independent electrochemical experiments. To the best of our knowledge, this is the first evidence on formation of xanthohumol dimers. The effect of the pH on the generation of oxidation products was further investigated. The monomeric and dimeric oxidation products are favored at pH of 5.5 and 4.5, respectively.

     

Synthesis, crystal structure, thermal and luminescence properties of CuX(2,3-dimethylpyrazine) (X=Cl, Br, I) coordination polymers

Three new coordination polymers based on CuI and 2,3-dimethylpyrazine (2,3-dmpyz) were prepared, structurally characterized and investigated for their thermal and luminescence properties. In the ligand rich 2:3 compound [(CuI)2(2,3-dmpyz)3] (CuI)2 dimers are found, which are connected by the N-donor ligands into chains, whereas in the structure of the 1:1 intermediate [(CuI)(2,3-dmpyz)] (CuI)4 tetramers are found, which are also connected into chains. The crystal structure of the ligand deficient 2:1 compound [(CuI)2(2,3-dmpyz)] is built up of CuI double chains, which are connected by the 2,3-dmpyz ligands into layers. Thermal decomposition of results in its direct transformation into the ligand deficient compound , without the formation of the 1:1 compound as an intermediate. A similar thermal reactivity is found for compound , which transforms into on heating. Stirring of a crystalline suspension of pure or in acetonitrile, always leads to a transformation into the ligand deficient compound indicating that compound is the most stable of all the coordination polymers, whereas compounds and are metastable. The luminescence properties of the CuCl and CuI coordination polymers were investigated at 298 and 77K. It was observed that the emission maxima strongly depends on the nature of the halide atom and the composition and structure of the coordination polymers. In addition, several of these compounds show luminescence thermochromism. These results are compared with those obtained for the previously reported CuCl and CuBr(2,3-dimethylpyrazine) coordination polymers.     

Identification of potential sources of thymoquinone and related compounds in Asteraceae, Cupressaceae, Lamiaceae, and Ranunculaceae families

In this study, forty-seven plant species belonging to seven families were analysed by GC and GC-MS for the contents of pharmacologically effective quinones: dithymoquinone (DTQ), thymohydroquinone (THQ), and thymoquinone (TQ). The results showed that detectable amounts (??1 mg kg^?1) of at least one of these compounds have been found in three species of both Monarda (M. didyma, M. media, and M. menthifolia) and Thymus (T. pulegioides, T. serpyllum, and T. vulgaris) genera, two Satureja (S. hortensis and S. montana) species, and in single representatives of Eupatorium (E. cannabinum), Juniperus (J. communis), and Nigella (N. sativa) genera. The maximum contents of THQ and TQ were found in M. media aerial parts and M. didyma inflorescences (2674 and 3564 mg kg^?1 of dried weight, respectively) in amounts significantly exceeding their maximum contents in N. sativa seeds (THQ = 530 mg kg^?1 and TQ = 1881 mg kg^?1), which are generally considered as the main natural source of both of these compounds. As a conclusion, M. didyma (bergamot) and M. media (purple bergamot) can be recommended as new prospective natural sources of THQ and TQ for pharmaceutical or food industries.