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.     

Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine

Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λ_ex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λ_ex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes.     

Chemical Composition and Biological Activity of Argentinian Propolis of Four Species of Stingless Bees

The chemical composition of propolis of four species of stingless bees (SLBs) from Argentina was determined, and its antibacterial and anticancer activity was evaluated on selected types of microbes and cancer cell lines. Volatile secretions of all propolis samples are formed by 174 C₂–C₁₅ organic compounds, mainly mono- and sesquiterpenes and their derivatives. The chromatograms of ether extracts showed 287 peaks, of which 210 were identified. The most representative groups in the extracts of various propolis samples were diterpenoids (mainly resin acids), triterpenoids and phenolic compounds: long-chain alkenyl phenols, resorcinols and salicylates. The composition of both volatile and extractive compounds turned out to be species-specific; however, in both cases, the pairwise similarity of the propolis of Scaptotrigona postica and Tetragonisca fiebrigi versus that of Tetragona clavipes and Melipona quadrifasciata quadrifasciata was observed, which indicated the similarity of the preferences of the respective species when choosing plant sources of resin. The composition of the studied extracts completely lacked flavonoids and phenolcarboxylic acids, which are usually associated with the biological activity and medicinal properties of propolis. However, tests on selected microbial species and cancer cell lines showed such activity. All propolis samples tested against Paenibacillus larvae, two species of Bacillus and E. coli showed biofilm inhibition unrelated to the inhibition of bacterial growth, leading to a decrease in their pathogenicity. Testing the anticancer activity of ether extracts using five types of cell cultures showed that all four types of propolis studied inhibit the growth of cancer cells in a dose- and time-dependent manner. Propolis harvested by T. clavipes demonstrated the highest cytotoxicity on all tested cell lines.     

Sub-Nominal Resolution Fourier Transform Spectrometry with Chip-Based Combs

Chip-based optical frequency combs address the demand for compact, bright, coherent light sources of equidistant phase-locked lines. Traditionally, the Fourier Transform Spectroscopy (FTS) technique is considered a suboptimal choice for resolving comb lines in chip-based sensing applications due to the requirement of long optical delays, and spectral distortion from the instrumental line shape. Here, a sub-nominal resolution FTS technique is developed that extracts the comb's offset frequency in any spectral region directly from the measured interferogram without resorting to nonlinear $$-to- $$ interferometry. This in turn enables 10's of MHz resolution spectrometry with millimeter optical retardations currently limited by the emission linewidth and phase noise of the used lasers. Low-pressure Doppler-broadened absorption lines probed by widely-tunable chip-scale mid-infrared optical frequen with electrical pumping are fully resolved over a span of tens of nanometers. This versatile technique paves the way for compact, electrostatically-actuated, or even all-on-chip high-fidelity FTS, and can be readily applied to boost the resolution of existing commercial instruments with compact interferometers several hundred times.     

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.