Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH₂P(t-C₄H₉)₂)₂C₆H₄) and acidic [LWH(CO)₃] (L = Cp (1a), Tp (1b); Cp = η⁵-cyclopentadienyl, Tp = κ³-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me₂NHBH₃, ^tBuNH₂BH₃) dehydrogenation. The combination of variable-temperature (¹H, ³¹P{¹H}, ¹¹B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η¹-borane complex [(PCP)Pd(Me₂NHBH₃)]⁺[LW(CO₃)]⁻ (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.

Bimetallic complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H₂ evolution from two neutral hydrides.     

Nitropyridines as 2π-Partners in 1,3-Dipolar Cycloadditions with N-Methyl Azomethine Ylide: An Easy Access to Condensed Pyrrolines

1,3-Dipolar cycloaddition reactions of 2-substituted 5-R-3-nitropyridines and isomeric 3-R-5-nitropyridines with N-methyl azomethine ylide were studied. The effect of the substituent at positions 2 and 5 of the pyridine ring on the possibility of the [3+2]-cycloaddition process was revealed. A number of new derivatives of pyrroline and pyrrolidine condensed with a pyridine ring were synthesized.     

A Regioselective Synthesis of Novel Functionalized Organochalcogen Compounds by Chalcogenocyclofunctionalization Reactions Based on Chalcogen Halides and Natural Products

The regioselective synthesis of novel functionalized condensed organochalcogen compounds by chalcogenocyclofunctionalization reactions based on chalcogen halides and the natural products thymol and carvacrol has been developed. The reactions of selenium dibromide with allyl thymol and allyl carvacrol proceeded in methylene chloride at room temperature in the presence of NaHCO₃ affording bis[(7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] and bis[(4-isopropyl-7-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] selenides in 90–92% yield. Similar sulfides were obtained in 70–72% yields by the reaction of sulfur dichloride in chloroform under reflux. Trihalotellanes containing the same organic moieties were synthesized from allyl thymol, allyl carvacrol and tellurium tetrachloride or tetrabromide in quantitative yields. Corresponding functionalized ditellurides were prepared in 91–92% yields by the reduction of the trichlorotellanes with sodium metabisulfite in two-phase solvent system. The comparison of reactivity of sulfur, selenium and tellurium halides in chalcogenocyclofunctionalization and distinguishing features of each reaction were discussed.     

Gas-sensitive properties of thin nickel oxide films

The results of a study of the gas-sensitive properties of nickel oxide layers with respect to n-hexane, acetone, ethanol, benzene, o-xylene, toluene and ammonia are presented. NiO layers 100 ± 5 nm thick were obtained by chemical vapor deposition in the systems (EtCp)₂Ni–О₂–Ar and (EtCp)₂Ni–О₃–О₂–Ar. The electrical resistance of the layers changes in the presence of hexane, ethanol, benzene, and ammonia vapors. The electrical resistance of the obtained layers changed in the presence of vapors of hexane, ethanol, benzene and ammonia. Response and recovery time of the sensing element of the gas sensors did not exceed 6 s in the temperature range 500–600 K.     

Spectral Photoluminescent Parameters of Barley Seeds (Hordéum vulgáre) Infected with Fusarium ssp

We needed effective and sustainable technologies for better microbiological control of crops, including Fusarium. However, photoluminescent UV–Vis methods are potential for diagnosing plant diseases with Fusarium. It has not been sufficiently studied despite the application of these methods for other biological researches. The excitation spectrum of the seeds during infection shifts to the shorter wavelength and a new maximum appears in the region λ ≈ 232 nm. The photoluminescence of infected seeds increases with excitation by radiation of wavelengths λ_e,1 = 232 nm, λ_e,2 = 362 nm and λ_e,3 = 424 nm by 1.33–3.14 times, and λ_e,3 = 424 nm—decreases by 1.1 times. Statistical moments μ₃ and μ₄, asymmetry and kurtosis change only with short-wave excitation. When analyzing the decomposition of the frequency spectrum into Gaussian curves, the most informative ratio is the ratio of right-handed and left-handed Gaussians under excitation λ_e,2 = 362 nm and λ_e,3 = 424 nm. The ratios of their maxima change during infection by 1.36–3.2 times, and for excitation by radiation λ_e,2, the frequency boundaries of Gaussians change. The results of measurements and calculations provide a basis for the development of a method and device for photoluminescence diagnostics of fusarium seeds in UV–Vis ranges.     

Cosmetic Formulations with Melaleuca alternifolia Essential Oil for the Improvement of Photoaged Skin: A Double-Blind,Randomized, Placebo-Controlled Clinical Study

This aim of this study was to evaluate the penetration depth, antioxidant capacity and the clinical efficacy of Melaleuca alternifolia pure essential oil and in a nanoemulsion to prevent skin photoaging. For this, 2% of pure essential oil or 2% of this essential oil in a nanoemulsion were vehiculated in a formulation. The skin penetration was evaluated using confocal Raman microspectroscopy. The radical protection factor was evaluated using electron paramagnetic resonance spectroscopy. For a clinical study, 40 male participants, aged 18–28 years, were enrolled, being divided into three groups: vehicle formulation, M. alternifolia pure essential oil and M. alternifolia Nanoemulsion. All the participants also received a sunscreen SPF 50 to use during the day. Before and after 90 days of study, skin hydrolipidics and morphological characteristics were performed by skin imaging and biophysical techniques. The nanoemulsion presented a lower antioxidant capacity and a higher penetration through the stratum corneum, reaching the viable epidermis, improving the stratum granulosum morphology. The groups presented an increase in the papillary depth, improving in the dermis echogenicity and the collagen fibers. Melaleuca alternifolia essential provides the potential to improve photoaged skin, being the application of nanoemulsion able to reach deeper skin layers.     

Magnetopolaron states involving confined phonons in a semiconductor quantum well

Energy splitting ΔE _res in double magnetopolaron energy spectrum in rectangular quantum wells as functions of the well width d have been calculated. We have considered in the capacity of interaction leading to resonant coupling between electrons and phonons the interaction with confined phonons and (for comparison) with bulk LO phonons. We have obtained the conditions when the interaction with bulk phonons yields correct results. Calculations for AlAs/GaAs/AlAs and AlSb/InSb/AlSb structures have been performed. Alongside the parameter ΔE _res for a polaron, whose resonant magnetic field is determined by the condition Ω=ω _L1, where Ω is the cyclotron frequency and ω _L1 is the LO phonon frequency in the quantum well (A-polaron), we have calculated ΔE _res for D-(Ω=2ω _L1) and F-polarons (Ω=3ω _L1), which is a factor of $\sqrt 2 $ and $\sqrt 3 $ , respectively, smaller than ΔE _res for the A-polaron. Since the splitting ΔE _res for the A-polaron is very large (up to 0.2?ω _L1), it is more convenient to study in experiments D-and F-polarons since their resonant magnetic fields are lower. We have predicted existence of “weak” magnetopolarons, in which the splitting is proportional to a higher power of Frölich’s coupling constant α than α ^1/2.     

Local magnetization of Co andMn impurities in the reentrant spin glass Au0.82Fe0.18

The low-temperature nuclear orientation technique has been used to study the magnetic behaviour of⁶⁰Co and⁵⁴Mn impurity atoms in the reentrant spin glass Au_0.82Fe_0.18. The results obtained for⁶⁰Co indicate that Co moments follow the distribution of Fe directions. In contrast, Mn moments show a spread directional distribution. These results are the consequence of the different character of Mn-Fe andFe-Fe interactions at short distances.     

Scalar electrodynamics and the theory of a neutral vector field in the dispersion approach

Theoretical and Mathematical Physics -