Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations

A model for studying polar-pi interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (DeltaG(not equal) vs. sigma(0)). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.     

Imidazolyl derivatives of the chroman ring. 2

The synthesis of 3-(1H-imidazol-1-yl)-4H-1-benzopyran-4-ones 2 and of 2-(1H-imidazol-1-yl)-4H-1-benzopyr-an-4-ones 11 are described. The former proceeds through chroman ring closure from 2-(1H-imidazol-1-yl)-2′-hydroxyacetophenones, the latter occurs reacting 3-bromo-4H-1-benzopyran-4-ones with imidazole and represents an example of a new synthesis of 2-heteroarylchromones. Compounds 2 can be easily reduced to the corresponding chromanones and chromanols previously described in Part 1.     

Determination of different forms of aminothiols in red blood cells without washing erythrocytes

Detection and quantification of different aminothiols forms (reduced and total) in biological fluids are important for the investigation of oxidative stress‐related diseases and cell homeostasis study. The aim of this study was to optimize a HPLC method in order to determine both reduced and total thiol forms in red blood cells (RBC) at low temperature without washing erythrocytes. Analytical recoveries for total and reduced thiols were 91.6–98.5 and 94.9–98.2% respectively. The relative standard deviations intra‐assay for total and reduced thiols were 1.14–3.64 and 0.83–2.3% respectively and the relative standard deviations inter‐assay for total and reduced thiols were 1.12–3.54 and 0.84–2.03%, respectively. This method allows specific analysis of the aminothiol state inside the RBC, as a model of intracellular metabolism functioning. Copyright © 2013 John Wiley & Sons, Ltd.