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Benchmarking tactical positioning of business and IT tactics: possibilities, pitfalls, problems along with options.
New types of cyclic diazo compounds capable of Rh(II)-catalyzed spirocyclizations with tetrahydrofuran have been discovered. The formation of the spirocyclic framework is thought to proceed via the formation of Rh(II) carbene species followed by interaction with the Lewis basic oxygen atom of tetrahydrofuran to give oxonium ylide species. The latter evolves predominantly via the Stevens type rearrangement leading to an [n + 1] ring expansion of the tetrahydrofuran moiety, which results in the formation of a medicinally relevant 6-oxa-2-azaspiro[4.5]decane scaffold. The spirocyclization process was often observed in competition with mechanistically distinct C-H insertion into a tetrahydrofuran molecule. This competing process gave compounds based on the 3-(tetrahydrofur-2-yl)pyrrolidine scaffold, which are also relevant from the medicinal chemistry standpoint. These findings enrich the available arsenal of metal-catalyzed spirocyclization methods based on the use of cyclic diazo compounds.4'-N,N-Dimethylamino-3-hydroxyflavone (DMAHF), a synthetic fluorescent flavone analogue with potent antioxidant activity, was explored as a molecular rotor-like fluoroprobe for amyloid aggregations, a causative factor in Alzheimer's disease, Parkinson's disease, type-2 diabetes, etc. During its interactions with (human) insulin amyloid aggregation (IAA), its microenvironment was changed. This instigated a drastic change in its excited-state intramolecular proton transfer-based dual emission behavior, which was tracked to monitor its amyloid probing activity. Thus, the amyloid probing potential of DMAHF was originated from its interactions with IAA, which were studied by various spectroscopic techniques and molecular docking and quantum-mechanical calculations. Morphological changes of the IAA in the presence of DMAHF were studied by scanning electron microscopy. DMAHF also probed efficiently the islet amyloid polypeptide deposition in the pancreatic β-cells of diabetic mice. DMAHF showed significant sensitivity and specificity towards amyloid aggregation without having any complexity in its photophysical behavior. This indicates its potential as an ideal bio-friendly and cost-effective fluoroprobe for amyloid proteins.Dual activation of both C-I and vicinal C-H bonds of diaryliodonium salts allowing for diarylation is a subject of rapid construction of π-extended frameworks. Here, we report palladium-catalyzed cascade of C8-arylation/intramolecular Friedel-Crafts acylation of α-naphthoic acids in the synthesis of benzanthrone derivatives. The step-economical protocol tolerates various substrates, which resulted in a potential molecular library for developing functional polycyclic scaffolds. The approach relies on the synergistic action of strong acid with palladium catalysts to form two bonds in a one-pot procedure.We report several novel thermometers resulting from the temperature-induced aggregation of difluoroboron β-diketonate chromophores. These thermometers exhibit a much wider temperature-dependent fluorescence emission from 445 to 592 nm along with the color change from blue to red in a dilute chloroform solution. Spectroscopy measurements and theoretical calculations confirm that the thermochromic luminescence originates from the reversible change in the noncovalent intermolecular interactions and the abrupt volume shrinkage of the solvent at its melting point. The present work provides a new strategy for rationally designing high-performance thermometers having a wide emission property.In order to study the wetting behavior of a liquid film on a surface with ultralow contact angle, the interference fringe method with oblique upward laser is developed. WS6 research buy This method allows us to detect the position of contact line precisely and observe the surface profile of very thin film. The contact angle measurement is verified within from 0.007° to 3°. The wetting behavior of silicone oil droplet on a glass substrate is observed. The wetting process can be distinguished with three stages, such as advancing, stable ,and receding stage. In the stable stage, there are two angles near the contact line. And the two angles have opposite variations in trend. It can be seen that there are some reciprocating changes in the two angles and the thickness of the liquid film near the contact line during the stable stage, like the edge of the surf.In this work, a novel strategy for the straightforward synthesis of substituted phthalimides is described, which includes base-mediated Michael addition/intramolecular cyclization/[1,5]-H shift/cleavage of CS2/aromatization/nucleophilic acyl substitution reaction of 2-(4-oxo-2-thioxothiazolidin-5-ylidene)acetates and α,α-dicyanoolefines under ultrasound (US) irradiation. Some advantages of this method are as follows having simple operation, easily accessible starting materials, chemoselective cascade process, synthetically useful yields, and green conditions by utilizing US irradiation as a source of energy and using ethanol as solvent.A visible-light-induced reaction of an O3-trimethylamine (TMA) complex isolated in low-temperature noble-gas matrices is investigated by infrared (IR) and visible absorption spectroscopies using the DFT calculation. The complex isolated in a Ne matrix yields trimethylamine-N-oxide (TMAO) upon irradiation (λ ≥ 800 nm) by dissociation of O3. When the wavelength of radiation is changed to λ = 455 nm, two stable conformers of dimethylaminomethanol (DMAM) are recognized besides TMAO. In an Ar matrix, DMAM and not TMAO is mainly produced upon λ = 455 nm irradiation. The photoreaction mechanism of the O3-TMA complex with a single collision reaction between O(3P) and TMA in the gas phase to produce OH and CH2N(CH3)2 radicals is discussed.Inspired by the photochemical mechanism of a plant blue-light receptor, a unique flavin-based photocatalytic system was developed for the chemoselective heterocoupling of two different thiols, which enabled the facile synthesis of unsymmetrical disulfides. Owing to the redox- and photo-organocatalysis of flavin, the coupling reaction took place under mild metal-free conditions and visible light irradiation with the use of air, which is recognized as the ideal green oxidant.
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