A series of OLED-relevant compounds, consisting of 1,3,5-triazine core linked to various aromatic arms by amino group, has been synthesized and characterized. The studied compounds exist in solution as a mixture of two conformers, a symmetric propeller and asymmetric conformer, in which one of the aromatic arms is rotated around the C-N bond. At temperatures below −40 °C, the VT NMR spectra in DMF-d7 are in a slow exchange regime, and the signals of two conformers can be elucidated. At temperatures above 100 °C, the VT NMR spectra in DMSO-d6 are in a fast exchange regime, and the averaged spectra can be measured. The ratio of symmetric and asymmetric conformers in DMF-d7 varies from 14:86 to 50:50 depending on the substituents. The rotational barriers of symmetric and asymmetric conformers in DMF-d7 were measured for all compounds and are in the interval from 11.7 to 14.7 kcal/mol. The ground-state energy landscapes of the studied compounds, obtained by DFT calculations, show good agreement with the experimental rotational barriers. The DFT calculations reveal that the observed chemical exchange occurs by the rotation around the C(1,3,5-triazine)-N bond. Although some of the compounds are potentially tautomeric, the measured absorption and emission spectra do not indicate proton transfer neither in the ground nor in the excited state.

Gamma irradiation is efficiently applied to many foods, but nevertheless there is a distinct lack of information about the changes of macro- and micronutrients (e.g., carbohydrates, lipids, organic acids, and phenolics) in dried rose hip (RH) fruits. Therefore, in this study, for the first time, the effect of gamma irradiation (10 and 25 kGy) on RH constituents is investigated. Different analytical techniques (GC-FID, HPLC-UV, HPSEC-RID, IR-FT, and SEM) are employed to examine this effect. The irradiation treatment (10 kGy) increased the glucose content by 30% and released cellobiose from RH fruits, thus revealing cellulose destruction. The extractability of total uronic acids increased from 51% (control) to 70.5% (25 kGy-irradiated), resulting in a higher pectin yield (10.8% < 12.8% < 13.4%) and molecular heterogeneity. Moreover, de-esterification was not a major effect of the irradiation-induced degradation of pectin. The sample exposure to the highest dose did not change the content of total carotenoids, β-carotene, and (un)saturated fatty acids, but it affected the tocopherols levels. Gamma rays had a negligible effect on the phenolic constituents and did not affect ORAC and HORAC antioxidant activity. In conclusion, it can be compromised that the exposition of dried RH is safe and can be successfully applied to decontaminate fruits without affecting their nutritional value and biological activity.

A series of squaric acid amides (synthesized in 66–99% isolated yields) and a set of chiral aminoalcohols were comparatively studied as ligands in a model reaction of reduction of α-chloroacetophenone with BH3•SMe2. In all cases, the aminoalcohols demonstrated better efficiency (up to 94% ee), while only poor asymmetric induction was achieved with the corresponding squaramides. A mechanistic insight on the in situ formation and stability at room temperature of intermediates generated from ligands and borane as possible precursors of the oxazaborolidine-based catalytic system has been obtained by 1H DOSY and multinuclear 1D and 2D (1H, 10/11B, 13C, 15N) NMR spectroscopy of equimolar mixtures of borane and selected ligands. These results contribute to better understanding the complexity of the processes occurring in the reaction mixture prior to the possible oxazaborolidine formation, which play a crucial role on the degree of enantioselectivity achieved in the borane reduction of α-chloroacetophenone.

Modern supercritical fluid chromatography (SFC) is now a well-established technique, especially in the field of pharmaceutical analysis. We recently demonstrated the transferability and the reproducibility of a SFC-UV method for pharmaceutical impurities by means of an inter-laboratory study. However, as this study involved only one brand of SFC instrumentation (Waters®), the present study extends the purpose to multi-instrumentation evaluation. Specifically, three instrument types, namely Agilent®, Shimadzu®, and Waters®, were included through 21 laboratories (n = 7 for each instrument). First, method transfer was performed to assess the separation quality and to set up the specific instrument parameters of Agilent® and Shimadzu® instruments. Second, the inter-laboratory study was performed following a protocol defined by the sending lab. Analytical results were examined regarding consistencies within- and between-laboratories criteria. Afterwards, the method reproducibility was estimated taking into account variances in replicates, between-days and between-laboratories. Reproducibility variance was larger than that observed during the first study involving only one single type of instrumentation. Indeed, we clearly observed an 'instrument type' effect. Moreover, the reproducibility variance was larger when considering all instruments than each type separately which can be attributed to the variability induced by the instrument configuration. Nevertheless, repeatability and reproducibility variances were found to be similar than those described for LC methods; i.e. reproducibility as %RSD was around 15 %. These results highlighted the robustness and the power of modern analytical SFC technologies to deliver accurate results for pharmaceutical quality control analysis.

A series of 60 nitrobenzonitrile analogues of the anti-viral agent MDL-860 were synthesized (50 of which are new) and evaluated for their activity against three types of enteroviruses (coxsackievirus B1, coxsackievirus B3 and poliovirus 1). Among them, six diaryl ethers (20e, 27e, 28e, 29e, 33e and 35e) demonstrated high in vitro activity (SI > 50) towards at least one of the tested viruses and very low cytotoxicity against human cells. Compound 27e possesses the broadest spectrum of activity towards all tested viruses in the same way as MDL-860 does. The most active derivatives (27e, 29e and 35e) against coxsackievirus B1 were tested in vivo in newborn mice experimentally infected with 20 MLD50 of coxsackievirus B1. Compound 29e showed promising in vivo activity (protection index 26% and 4 days lengthening of mean survival time). QSAR analysis of the substituent effects on the in vitro cytotoxicity (CC50) and anti-viral activity of the nitrobenzonitrile derivatives was carried out and adequate QSAR models for the anti-viral activity of the compounds against poliovirus 1 and coxsackievirus B1 were constructed.

The application of super-critical carbon dioxide extraction of rose hip (Rosa canina L.) seeds for production of high quality oil was explored. For the purpose, main oil characteristics as fatty acids composition, tocopherols and carotenoids contents, as well as the oil oxidative stability were evaluated. The results revealed that technological conditions as pressure (350-450 bar) and particles size of the milled seeds (0.4, 1 mm) did not practically affect the fatty acids composition. However, increasing the pressure from 350 to 400 bar caused slight increasing of tocopherols and carotenes contents whereas decreasing of particles size reduced their amounts. The higher quantity of these antioxidants insured better oxidative stability of the rose hip oil and thence its high quality.

The synthesis of new enantiopure N-acyl compounds derived from (-)-fenchone has been performed. The evaluation of their in vitro activity against Mycobacterium tuberculosis H37Rv showed for most of them moderate activity. The structures bearing sulfonamide functionality have comparable activity to ethambutol and possess low cytotoxicity.

The synthesis of 22 structurally diverse urea, thiourea and acylthiourea derivatives containing the (R)-2-amino-1-butanol motif has been performed. The evaluation of their in vitro activity against Mycobacterium tuberculosis (H(37)Rv and strain 43) showed promising results in the case of the acylthiourea derivatives (MIC range 0.36-7.46 mu M for H(37)Rv strain). (C) 2013 Elsevier Masson SAS. All rights reserved.