Easy, inexpensive and effective oxidative iodination of deactivated arenes in sulfuric acid

Two ‘model’ deactivated arenes, benzoic acid and nitrobenzene, were effectively monoiodinated within 1 h at 25-30 °C, with strongly electrophilic I⁺ reagents, prior prepared from diiodine and various oxidants (CrO₃, KMnO₄, active MnO₂, HIO₃, NaIO₃, or NaIO₄) in 90% (v/v) concd sulfuric acid (ca. 75 mol% H₂SO₄). Next, an I₂/NaIO₃/90% (v/v) concd H₂SO₄ exemplary system was used to effectively mono- or diiodinate a number of deactivated arenes. All former papers dealing with the direct iodination of deactivated arenes are briefly reviewed.     

Electron collisions with trifluorides: BF3 and PF3 molecules

Absolute total cross sections (TCSs) for electron scattering from boron trifluoride (BF(3)) and phosphorus trifluoride (PF(3)) molecules have been measured using a linear transmission method. The electron energy ranges from 0.6 to 370 eV for BF(3) and from 0.5 to 370 eV for PF(3). The TCS energy dependence for BF(3) exhibits two very pronounced enhancements: resonantlike narrow feature located near 3.6 eV with the maximum value of 19.2 x 10(-20) m(2), and intermediate energy very broad enhancement with two humps, one centered around 21 eV (18.8 x 10(-20) m(2) in the maximum) and the other near 45 eV (19.5 x 10(-20) m(2)). For PF(3) the TCS has quite different low-energy dependence: at 0.5 eV it has a high value of 70 x 10(-20) m(2) and decreases steeply towards higher energies. Beyond the minimum near 5.5 eV, the TCS reveals two distinct humps: the resonant one centered near 11 eV with the peak value of 32.9 x 10(-20) m(2) and the second one much broader around 35 eV (27.9 x 10(-20) m(2)). The present TCSs for trifluorides are compared to each other as well as to previous TCS data for selected perfluorides and to results for their perhydrided counterparts. The differences and similarities in the shape and magnitude of TCSs are pointed out.     

Selective Reduction of the N-O Bond in Heteroaromatic N-Oxides by TiCl4/SnCl2

Heteroaromatic N-oxides bearing various functionalities are readily and selectively converted under mild conditions into the corresponding bases using TiCl₄/SnCl₂.     

Electrochemical Behavior of Cobaltocene in Ionic Liquids

The electrochemical behavior of cobaltocenium has been studied in a number of room temperature aprotic ionic liquids. Well defined, diffusion controlled, anodic and cathodic peaks were found for the Cc⁺/Cc (cobaltocenium/cobaltocene) reduction/oxidation on gold, platinum and glassy carbon electrodes. Values of the peak separation parameters suggest quasireversibility or even irreversibility for the redox process. The difference between the ferrocene/ferrocenium and cobaltocenium/cobaltocene couples has been evaluated as equal to (1.350 ± 0.020) V. Values of the cobaltocenium (Cc⁺) diffusion coefficients D have been calculated on the basis of the Randles–Sevcik equation.     

[11]Anthrahelicene on TiO2 surfaces

Helicenes are carbon-rich materials with an ordered structure that possess interesting and remarkable electronic, chiroptical, mechanical and magnetic properties either in bulk or as single molecule devices. We report on the first attempt to anchor and organize [11]anthrahelicene ([11]AH) molecules onto a metal oxide surface. Molecular structures obtained on the (110) and (011) faces of rutile titania are characterized using scanning probe microscopy. On the (110) surface, [11]AH molecules form islands that are comprised of small domains of two types that are mirror reflections of each other and have an ordered quasi-hexagonal lattice. In contrast, molecules form unordered clusters on the (011) surface. Single molecules on both faces are imaged with sub-molecular resolution.     

Multicomponent Peptide Stapling as a Diversity‐Driven Tool for the Development of Inhibitors of Protein–Protein Interactions

Stapled peptides are chemical entities in‐between biologics and small molecules, which have proven to be the solution to high affinity protein–protein interaction antagonism, while keeping control over pharmacological performance such as stability and membrane penetration. We demonstrate that the multicomponent reaction‐based stapling is an effective strategy for the development of α‐helical peptides with highly potent dual antagonistic action of MDM2 and MDMX binding p53. Such a potent inhibitory activity of p53‐MDM2/X interactions was assessed by fluorescence polarization, microscale thermophoresis, and 2D NMR, while several cocrystal structures with MDM2 were obtained. This MCR stapling protocol proved efficient and versatile in terms of diversity generation at the staple, as evidenced by the incorporation of both exo‐ and endo‐cyclic hydrophobic moieties at the side chain cross‐linkers. The interaction of the Ugi‐staple fragments with the target protein was demonstrated by crystallography.     

Sample Preparation Methods for Lipidomics Approaches Used in Studies of Obesity

Obesity is associated with alterations in the composition and amounts of lipids. Lipids have over 1.7 million representatives. Most lipid groups differ in composition, properties and chemical structure. These small molecules control various metabolic pathways, determine the metabolism of other compounds and are substrates for the syntheses of different derivatives. Recently, lipidomics has become an important branch of medical/clinical sciences similar to proteomics and genomics. Due to the much higher lipid accumulation in obese patients and many alterations in the compositions of various groups of lipids, the methods used for sample preparations for lipidomic studies of samples from obese subjects sometimes have to be modified. Appropriate sample preparation methods allow for the identification of a wide range of analytes by advanced analytical methods, including mass spectrometry. This is especially the case in studies with obese subjects, as the amounts of some lipids are much higher, others are present in trace amounts, and obese subjects have some specific alterations of the lipid profile. As a result, it is best to use a method previously tested on samples from obese subjects. However, most of these methods can be also used in healthy, nonobese subjects or patients with other dyslipidemias. This review is an overview of sample preparation methods for analysis as one of the major critical steps in the overall analytical procedure.