Fast intramolecular charge transfer with a planar rigidized electron donor/acceptor molecule

The planar rigidized molecule fluorazene (FPP) undergoes fast reversible intramolecular charge transfer (ICT) in the excited state, with a reaction time of 12 ps in the polar solvent ethyl cyanide at -45 degrees C. The ICT state of FPP has a dipole moment mu(e)(ICT) of 13 D, much larger than that of the locally excited state LE (1 D). The ICT behavior of FPP is similar to that of its flexible counterpart N-phenylpyrrole (PP), for which mu(e)(ICT) = 12 D. These results show that intramolecular charge transfer to a planar ICT state can occur efficiently. In designing ICT systems capable of rapid switching, it is therefore important to realize that large amplitude motions such as those necessary for the formation of a twisted intramolecular charge transfer (TICT) state are not required.     

The Effect of Vibrational Excitation of Molecules on Plasmachemical Reactions Involving Methane and Nitrogen

An experimental study of plasmachemical reaction involving CH₄ and N₂ molecules in rf discharge was studied in order to know the effect of vibrational excitation of N₂ molecules. When the relative nitrogen concentration was greater than 0.8, the main product of CH₄ decomposition was HCN, and the rate of methane decomposition at this condition was faster than that one in pure methane. These results could be confirmed through the mass spectroscopic method. The reason for these results is the vibrational energy of N₂ excited by rf discharge. The chain reaction mechanisms of producing HCN by vibrational excitation of N₂ were examined closely through numerical simulation. The rate-controlling step was the dissociation reaction of excited nitrogen molecule to the atomic nitrogen, so the process of HCN synthesis was limited by the value of reaction constant, k^N.     

Experimental study of the gas-phase hydrofluorination of perchloroethylene over a chromium-based catalyst

Summary Gas-phase hydrofluorination of perchloroethylene to pentafluoroethane in the presence of a chromium-magnesium catalyst at 0.4 MPa and 330-390°C has been studied. А reaction scheme taking into account the formation of by-products is suggested. An erratum to this article is available at .     

The synthesis and characterisation of ferromagnetic CaMn2O4 nanowires.

The synthesis of marokite CaMn(2)O(4) nanowires using a hydrothermal method is reported. Transmission electron microscopy and electron diffraction measurements show that the nanowires are polycrystalline in nature with diameters between 10 and 20 nm and lengths ranging from approximately 100 to 500 nm. Most interestingly, in contrast with the bulk material, magnetization measurements show that these nanowires exhibit ferromagnetic ordering with a Curie temperature (T(C)) of approximately 40 K.     

Towards the development of multisensor for drugs of abuse based on molecular imprinted polymers

The synthetic receptors for cocaine, deoxyephedrine, methadone and morphine were computationally designed and produced using molecular imprinting. The structure and energy of the molecular complexes were analysed by computational techniques. The possible structures of the binding sites in the synthetic receptors have been compared with those of corresponding natural receptors. The composition of imprinted polymers was optimised to allow adequate performance under the same experimental conditions. All selected molecular imprinting polymers (MIPs) demonstrated stronger affinity in comparison with corresponding blank polymers resulting in imprinted factors (I) equal to 1.2 (cocaine), 2.5 (deoxyephedrine), 3.5 (methadone) and 3 (morphine) which suggested that the specific binding site for each molecule was successfully created. The polymers studied possessed good selectivity and affinity towards their templates and could be recommended for the integration with sensor devices. From a practical point of view, especially for multisensor requirements, the synthetic receptors based on imprinted polymers could be superior to natural receptors due to their stability, robustness and compatibility with automation processes required for sensor fabrication.     

Approximation issues of fractional knapsack with penalties: a note

4OR - Malaguti et al. introduce (Eur J Oper Res 273:874–888, 2019) the Fractional Knapsack Problem with Penalties, which is similar to the classical 0-1 Knapsack problem, except that each of...     

Kantorovich’s Fixed Point Theorem and Coincidence Point Theorems for Mappings in Vector Metric Spaces

Set-Valued and Variational Analysis - The fixed points and coincidence points of mappings of v-metric spaces, i.e., sets on which a vector metric is defined, are investigated. The values of such a...     

Transport properties and electroanalytical response characteristics of drotaverine ion-selective sensors

The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10^–6 to 5×10^–2 mol L^–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10^–6 mol L^–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography.     

Synthesis of 6H-pyrrolo[3',4':2,3][1,4]diazepino[6,7,1-hi]indole-8,10(7H,9H)-diones using 3-bromo-4-(indol-1-yl)maleimide scaffold

Series of 3-arylalkyl- or 3-alkylamino-4-(indol-1-yl)maleimides and bis(indol-1-yl)maleimides were synthesised. The cyclization of the 3-substituted 4-(indol-1-yl)maleimides under the action of acids resulted in the formation of diazepine[1,4] derivatives with indoline and maleimide nuclei annelated. These compounds readily produced the corresponding indolomaleimidodiazepines[1,4] after dehydrogenation.     

General and efficient insertion of carbons carrying benzotriazole

Anions formed from the lithiation of 1-(1-benzotriazolylalkyl)benzotriazoles (1, 6) and 1-(1-methylthioalkyl)benzotriazoles (10 and 10a) with n-BuLi underwent additions to cyclic and acyclic ketones giving intermediates 3a-f, 7b-f, and 11b-d, respectively, in excellent yields. Thermal rearrangements of intermediates 3a,b,d-f and 7b-d,f in the presence of zinc bromide provided one-carbon chain-extended or ring-expanded alpha-benzotriazolyl ketones 4a,b,d-f and 8b-d,f in moderate yields with excellent regioselectivity. By contrast, intermediates 11b-d on treatment with zinc bromide loose a molecule of benzotriazole followed by intramolecular cyclization of the resulting intermediates 12b-d to provide the 2,3- and 1,2,3-substituted indenes 13b-d in good yields.