Tetrapyridoxycalix[4]arene and its copper(II) complex: an ionic crystal engineering tecton for self-inclusion polymers

The crystal structures of a tetradentate pyridylcalix[4]arene ligand and its first copper(II) complex are discussed. The metal free ligand is mainly self-assembled by dipole–dipole interactions and a combination of CH–N bonds and CH–π interactions. The corresponding copper(II) perchlorate complex exhibits a self-inclusion behaviour to supramolecular zig-zag polymers.     

Detector based on time-resolved ion-induced voltage in laser multiphoton ionization and laser-induced fluorescence

The time-resolved ion-induced voltages obtained from multiphoton ionization (MPI) in gases were applied, for the first time, together with time-resolved laser-induced fluorescence (TR-LIF) for fast detection of organic compounds in ambient air. The target compounds were polycyclic aromatic hydrocarbons (PAHs) and nitroaromatics. The concepts of the proposed method are presented and examined. It is shown that the MPI signals allow for estimation of the molecular weight, while the fluorescence data supply additional quantitative and qualitative information. A 3D data presentation is suggested for obtaining selectivity. The proposed dimensions are the MPI-based mass estimation, the maximum LIF wavelength and the measured fluorescence lifetime. Since all required data are acquired simultaneously and since the setup can be continuously operated, this analytical concept is suggested for on-line applications. The common air components are not ionized at the selected wavelengths and only the organic pollutants are detected under these conditions. Moreover, it is shown that the resonant MPI mode provides a certain level of selectivity. Therefore, this setup may become the basis of an air sniffer.     

Pyrimidine synthesis - A new method

A new one-step-method for the synthesis of 2-phenylpyrimidines of type I was developed by reacting benzotrichloride with various nitriles in the presence of aluminum chloride.     

Effect of synthesis conditions on the microstructure of TEOS derived silica hydrogels synthesized by the alcohol-free sol–gel route

Silica matrices synthesized from a pre-hydrolysis step in ethanol followed by alcohol removal at low pressure distillation, and condensation in water, are suitable for encapsulation of biomolecules and microorganisms and building bioactive materials with optimized optical properties. Here we analyze the microstructure of these hydrogels from the dependence of I(q) data acquired from SAXS experiments over a wide range of silica concentration and pH employed in the condensation step. From the resulting data it is shown that there is a clear correlation between the microscopic parameters—cluster fractal dimension (D), elementary particle radius (a) and cluster gyration radius (R)—with the attenuation of visible light when the condensation step proceeds at pH < 6. At higher pHs, there is a steep dependence of the cluster density (~R ^D−3) with the condensation pH, and non-monotonous changes of attenuance are less than 20%, revealing the complexity of the system. These results, which were obtained for a wide pH and silica concentration range, reinforce the idea that the behavior of gels determined in a restricted interval of synthesis variables cannot be extrapolated, and comparison of gelation times is not enough for predicting their properties.     

The synthesis of (Z)-trisubstituted allylic alcohols by the selective 1,4-hydrogenation of dienol esters: improved synthesis of (-)-β-santalol

(E)-Trisubstituted allylic alcohols are commonly prepared from the corresponding (E)-enals, themselves readily accessible by a simple aldol condensation reaction. We demonstrate that these very same (E)-enals can be converted into (Z)-trisubstituted allylic acetates (and thus alcohols) by a ruthenium-catalyzed 1,4-hydrogenation of the corresponding dienol acetates. This simple solution to a long-lasting problem was applied to an industrially feasible synthesis of (-)-β-santalol.     

Structural identification of SAR-943 metabolites generated by human liver microsomes in vitro using mass spectrometry in combination with analysis of fragmentation patterns

SAR-943 (32-deoxo rapamycin) is a proliferation signal inhibitor via interaction with the mammalian target of rapamycin (mTOR). Most importantly, SAR-943 has improved chemical stability compared to rapamycin (sirolimus) and is currently under investigation as a drug coated on coronary stents. It was the goal of this study to identify the SAR-943 metabolites generated after incubation with human liver microsomes using high-resolution mass spectrometry (MS) and MS/iontrap (MS(n)) and comparison of fragmentation patterns of the metabolites with those of SAR-943 and other known rapamycin derivatives. Our study showed that SAR-943 is mainly hydroxylated and/or demethylated by human liver microsomes. The structures of the following metabolites were identified: O-demethylated metabolites: 39-O-desmethyl, 16-O-desmethyl and 27-O-desmethyl SAR-943; hydroxylated metabolites: hydroxy piperidine SAR-943, 11-hydroxy, 12-hydroxy, 14-hydroxy, 23-hydroxy, 24-hydroxy, 25-hydroxy, 46-hydroxy and 49-hydroxy SAR-943; didemethylated metabolites: 16,39-O-didesmethyl and 27,39-O-didesmethyl SAR-943; demethylated-hydroxylated metabolites: 39-O-desmethyl, 23- or 24-hydroxy and 39-O-desmethyl, hydroxy piperidine SAR-943 and dihydroxylated metabolites: 12-,23- or 24-dihydroxy SAR-943. In addition, several other demethylated-hydroxylated and dihydroxylated metabolites were detected. However, their exact structures could not be identified.     

Two-step synthesis of hexaammonium triptycene: an air-stable building block for condensation reactions to extended triptycene derivatives

A simple two-step synthesis of an air-stable hexaammoniumtriptycene is introduced, which can be used for a variety of transformations by condensation reactions, e.g., to benzimidazole, benzotriazole, and quinoxaline derivatives in high yields.     

Synthesis of cis- and trans-3-aminocyclohexanols by reduction of β-enaminoketones

We describe a protocol developed for the preparation of β-enaminoketones derived from 1,3-cyclohexanediones, and their subsequent reduction by sodium in THF-isopropyl alcohol to afford cis- and trans-3-aminocyclohexanols.