Mechanism of Iodine(III)-Promoted Oxidative Dearomatizing Hydroxylation of Phenols: Evidence for a Radical-Chain Pathway

The oxidative dearomatization of phenols with the addition of nucleophiles to the aromatic ring induced by hypervalent iodine(III) reagents and catalysts has emerged as a highly useful synthetic approach. However, experimental mechanistic studies of this important process have been extremely scarce. In this report, we describe systematic investigations of the dearomatizing hydroxylation of phenols using an array of experimental techniques. Kinetics, EPR spectroscopy, and reactions with radical probes demonstrate that the transformation proceeds by a radical-chain mechanism, with a phenoxyl radical being the key chain-carrying intermediate. Moreover, UV and NMR spectroscopy, high-resolution mass spectrometry, and cyclic voltammetry show that before reacting with the phenoxyl radical, the water molecule becomes activated by the interaction with the iodine(III) center, causing the Umpolung of this formally nucleophilic substrate. The radical-chain mechanism allows the rationalization of all existing observations regarding the iodine(III)-promoted oxidative dearomatization of phenols.     

Thermodynamical evaluation of usefulness of future hydrocarbon fuels for use in compression ignition engines

The paper discusses the issues of the influence of the fuel spray formation on the generation of self-ignition spots and the development of pre-flame processes in the cylinder of a model diesel engine. The investigations were carried out for a standard diesel fuel and two other types of fuel that were mixtures of ethanol, butanol, and diethylether in a variety of proportions. By applying optical methods of analysis, the authors determined the geometrical indexes of the injected fuel spray as well as fuel mass distribution in the longitudinal and transverse cross section of the fuel spray during the injection process. The location and number of the self-ignition spots in the combustion chamber were evaluated on the basis of a comparison under various conditions: in presence of the charge swirl and at the lack of it. Research conducted for the single-cylinder engine confirmed the possibility of the use of diesel-like fuels for compression ignition engines.

     

Bioactive Phenolic Compounds from Primula veris L.: Influence of the Extraction Conditions and Purification

Our experiments may help to answer the question of whether cowslip (Primula veris L.) is a rich source of bioactive substances that can be obtained by efficient extraction with potential use as a food additive. A hypothesis assumed that the type of solvent used for plant extraction and the individual morphological parts of Primula veris L. used for the preparation of herbal extracts will have key impacts on the efficiency of the extraction of bioactive compounds, and thus, the health-promoting quality of plant concentrates produced. Most analysis of such polyphenolic compound contents in extracts from Primula veris L. has been performed by using chromatography methods such as ultra-performance reverse-phase liquid chromatography (UPLC−PDA−MS/MS). Experiments demonstrated that the most effective extraction agent for fresh study material was water at 100 °C, whereas for dried material it was 70% ethanol. The richest sources of polyphenolic compounds were found in cowslip primrose flowers and leaves. The aqueous and ethanol extracts from Primula veris L. were characterized by a quantitatively rich profile of polyphenolic substances, and a high antioxidative potential. Selective extraction with the use of mild conditions and neutral solvents is the first step to obtaining preparations from cowslip primrose with a high content of bioactive substances.     

Analysis of the Mechanism of Counter-current Spray Drying

Results of experimental investigations of the effect of drying and atomization parameters on counter-current spray drying are discussed. Based on 96 experimental tests, the local and global distributions of velocity, temperature, drying air humidity and moisture content of material dried in the drying tower were determined. Analysis of the results showed that the process of agglomeration during counter-current spray drying depended mainly on air temperature in the atomization zone.     

Synthesis and properties of a newly obtained sorbent based on silica gel coated with a polyaniline film as the stationary phase for non-suppressed ion chromatography

The new sorbent for non-suppressed ion chromatography based on silica gel coated with a film of polyaniline (PANI) was obtained in a process of in situ polymerization of aniline by oxidation with ammonium peroxydisulfate. Raman analyses performed using a Thermo Scientific DXR confocal Raman Microscope equipped with the Omnic 8 software from Thermo Fisher Scientific have proved a uniform distribution of PANI on the surface of chromatographic beads and in the pores of the particle.     

Performance of density functional theory in computing nonresonant vibrational (hyper)polarizabilities

A set of exchange‐correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM‐B3LYP, LC‐BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of all‐trans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the Møller–Plesset second‐order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM‐B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity‐dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro‐optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field‐induced second harmonic generation all of them, as well as the Hartree–Fock approximation, yield the wrong sign. We have also found that the Pople 6–31+G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry. © 2013 Wiley Periodicals, Inc.     

Modeling of timing belt construction

The frictional and profiling character of timing belt coupling with pulleys and the importance of surface state and workmanship accuracy of pulleys for the coupling quality have not been taken into account. In case of toothed cylindrical gears, operation tests have shown a huge significance of not only workmanship accuracy of pulleys, but also the technology of their working [1, 5]. Series of parameters essential for belt coupling with pulleys may be distinguished here, such as: profile of belt and pulley, surface state, barrel profile, whip and parallelism of shafts. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental study of light diffraction by standing ultrasonic wave with cylindrical symmetry

We report a new acousto-optic arrangement based on ultrasonic wave with cylindrical symmetry. The theory of light interaction with standing cylindrical ultrasonic wave is experimentally verified in the Fraunhofer region. A very good agreement of experimental results with numerical calculations based on the proposed theory is found. The diffraction pattern consists of ring-shaped diffraction orders which posses a fine structure. The time average light intensity of the whole zeroth diffraction order as a function of the Raman-Nath parameter is investigated. The modulation properties of presented system are examined by means of single photon counting technique. Finally, some potentially useful applications in the laser and fibre technology are suggested.     

Accurate Kohn–Sham ionization potentials from scaled‐opposite‐spin second‐order optimized effective potential methods

One important property of Kohn–Sham (KS) density functional theory is the exact equality of the energy of the highest occupied KS orbital (HOMO) with the negative ionization potential of the system. This exact feature is out of reach for standard density‐dependent semilocal functionals. Conversely, accurate results can be obtained using orbital‐dependent functionals in the optimized effective potential (OEP) approach. In this article, we investigate the performance, in this context, of some advanced OEP methods, with special emphasis on the recently proposed scaled‐opposite‐spin OEP functional. Moreover, we analyze the impact of the so‐called HOMO condition on the final quality of the HOMO energy. Results are compared to reference data obtained at the CCSD(T) level of theory. © 2016 Wiley Periodicals, Inc.