Gas chromatographic mass spectrometric assay for profiling the enantiomers of 3,4-methylenedioxymethamphetamine and its chiral metabolites using positive chemical ionization ion trap mass spectrometry

A qualitative GC/MS profile was obtained and its mass spectrometric features characterized for the analysis of the enantiomers of (RS)-3-4-methylenedioxymethamphetamin (MDMA) and its metabolites (RS)-3,4-methleenedioxyamphetamine (ha)A), (RS)-4-hydroxy-3-methoxymethamphetamine (HMMA) and (RS)-4-hydroxy-3-methoxyamphetamine (HMA). A chiral derivatization method was selected to obtain the diastereomers required for the separation of the respective enantiomers with a non-chiral GC stationary phase, The selected derivatization consisted of a reaction with N-heptafluorobutyryl-(S)-prolyl chloride combined with a consecutive reaction with N-methyl-N-trimethylsilyltrifluoroacetamide, resulting in N-[heptafluorobutyryl-(S)-prolyl]-O-trimethylsilyl derivatives, Detection was carried out with electron ionization and positive chemical ionization (PCI) ion trap mass spectrometry, Mass spectra of the derivatives of reference standards of the compounds of interest obtained with PCI demonstrated that this method simultaneously induces proton and charge-transfer reactions in the ion trap. The advantage is that high mass information is provided while some fragmentation remains to elucidate structural details, Subsequently; in three urine samples obtained from different and unrelated MDMA intoxications, the enantiomers of MDMA and MDA were identified. In some urine samples also HMMA and/or HMA were found, In addition to these compounds, an unexpected compound and/or additional chiral metabolite, N-hydroxy-(RS)-3,4-methylenedioxyamphetamine, was identified in two out of three urine samples, Preliminary results also indicated an enantioselective metabolism in the N-demethylation pathway for MDMA in humans. (C) 1997 John Wiley & Sons, Ltd

Low bandgap copolymers based on monofluorinated isoindigo towards efficient polymer solar cells

\u3cp\u3eTo explore the effectiveness of monofluorinated isoindigo as an electron-deficient building block in push-pull conjugated polymers for organic solar cell applications, four low bandgap copolymers are effectively synthesized and characterized. The effects of fluorine introduction, thiophene spacer length and polymer molar mass on the general electro-optical polymer characteristics, thin film blend microstructure and electronic performance are investigated. Isoindigo monofluorination effectively improves the power conversion efficiency from 2.8 up to 5.0% upon molar mass optimization, without using any processing additives or post-treatments.\u3c/p\u3

Differential regulated microRNA by wild type and mutant p53 in induced pluripotent stem cells

The tumour suppressor p53 plays an important role in somatic cell reprogramming. While wild-type p53 reduces reprogramming efficiency, mutant p53 exerts a gain of function activity that leads to increased reprogramming efficiency. Furthermore, induced pluripotent stem cells expressing mutant p53 lose their pluripotency in vivo and form malignant tumours when injected in mice. It is therefore of great interest to identify targets of p53 (wild type and mutant) that are responsible for this phenotype during reprogramming, as these could be exploited for therapeutic use, that is, formation of induced pluripotent stem cells with high reprogramming efficiency, but no oncogenic potential. Here we studied the transcriptional changes of microRNA in a series of mouse embryonic fibroblasts that have undergone transition to induced pluripotent stem cells with wild type, knock out or mutant p53 status in order to identify microRNAs whose expression during reprogramming is dependent on p53. We identified a number of microRNAs, with known functions in differentiation and carcinogenesis, the expression of which was dependent on the p53 status of the cells. Furthermore, we detected several uncharacterised microRNAs that were regulated differentially in the different p53 backgrounds, suggesting a novel role of these microRNAs in reprogramming and pluripotency