Effect of irradiation on ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate: an ESR study

Ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate [C₁₁H₁₅NO₂S] was synthesized by the Gewald method. Its single crystals were grown from an alcohol/ethyl acetate solution at 15 °C and characterized using IR and ¹H‐NMR. These single crystals were irradiated for 72 h at 298 K by a ⁶⁰Co gamma source with a dose speed of 0.864 kGy/h. After irradiation, electron spin resonance (ESR) measurements were carried out to study radiation‐induced radicals in the temperature range from 120 to 450 K. Additionally, for the single crystal, ESR angular dependencies were measured in the xy, xz and yz planes of the substance. This irradiated single crystal was analyzed based on the ESR spectra. Analysis of the spectra revealed that the radical was formed by a C–H bond fission at the carbon end of the substance. It was also observed that the color of the sample changed after irradiation. The hyperfine and g parameters were determined from the experimental spectra. It was inferred from these results that the hyperfine parameters and g value exhibited anisotropic behavior. The average values of these parameters were calculated as follows: g = 2.0088, A_H1=H2 = 20.70 G, A_H3=H4 = 10.80 G, A_Ha = 4.59 G, A_Hb = 3.24 G and, A_N = 6.10 G. Copyright © 2011 John Wiley & Sons, Ltd.     

Nitrogen/sulphur dual-doped hierarchical carbonaceous fibers boosting potassium-ion storage

The carbon materials as anode electrodes have been widely studied for potassium ion batteries(PIBs).However,the large size of potassium ions prevents their intercalation/deintercalation,resulting in poor storage behaviors.Herein,a novel design of N/S codoped hierarchical carbonaceous fibers(NSHCF)formed from nanosheets self-assembled by catalyzing Aspergillus niger with Sn is reported.The asprepared NSHCF at 600℃(NSHCF-600)exhibits a high reversible capacity of 345.4 m Ah g^-1 at 0.1 A g^-1 after 100 cycles and an excellent rate performance of 124.5 m Ah g^-1 at 2 A g^-1.The excellent potassium storage performance can be ascribed to the N/S dual-doping,which enlarges interlayer spacing(0.404 nm)and introduces more defects.The larger interlayer spacing and higher pyridinic N active sites can promote K ions diffusion and storage.In addition,the ex situ transmission electron microscopy reveals the high reversibility of potassiation/depotassiation process and structural stability.     

The periodic table of urea derivative: small molecules of zinc(II) and nickel(II) of diverse antimicrobial and antiproliferative applications

Molecular Diversity - Two complexes of Zn(II) and Ni(II) ions with the urea derivative, 2-benzimidazolyl-urea (BZIMU), of formulae [ZnBZIMU)2(H2O)](NO3)2 (1) and [Ni(BZIMU)2(CH3CH2OH)2](NO3)2 (2)...     

Effect of 165-keV Ar-ion irradiation on microstructural and mechanical properties of zircaloy-4

Journal of Radioanalytical and Nuclear Chemistry - Cold-worked zircaloy-4 was irradiated by 165 keV Ar ion at room temperature. The aim of the study is to understand the correlation...     

Determination of xylo-oligosaccharides in enzymatically hydrolysed pulp by liquid chromatography and capillary electrophoresis

Three different commercial β-1,4-endoxylanase preparations were used to hydrolyze bleached kraft pulp. Xylo-oligosaccharides in the produced filtrates were separated and quantified using both high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). All the determinations were performed without sample derivatization. The analytical methods were used to highlight the differences between the enzymes behaviour in terms of hydrolysates, but also to estimate the productivity of xylo-oligosaccharides from kraft pulp when the bleached material would be used in biorefining industry. The research showed that the glycosyl hydrolase family 10 enzyme produced by Aspergillus oryzae released xylobiose and xylotriose from the pulp material. The major oligosaccharides released by the family 11 enzyme produced by Bacillus sp. were xylotriose, xylobiose and xylotetraose. On the contrary, another family 11 enzyme produced by A. oryzae produced also xylose. The HPLC results agreed well with the xylose concentrations obtained after acid hydrolysis. The CE data showed the same trend, but much lower concentrations were identified than with HPLC. At the same time the HPLC method was able to separate only small oligosaccharides, whereas CE could be used for separation of all the xylo-oligosaccharides from xylobiose to xylohexaose. The highest xylo-oligosaccharide yield was achieved with Shearzyme at pH 5 corresponding to 22 % of total xylan from bleached birch kraft pulp.     

Crown Ether Complexes of Six-Membered N-heteroaromatic Cations

Crown ether complexes of six-membered N-heteroaromatic cations and the closely related bicyclic purinium cation (6) have been studied by ¹H NMR, mass spectrometric and crystallographic methods. The stability constants for the complexes were determined by ¹H NMR titration in acetonitrile solution and the complexation stoichiometry by ¹H NMR and ESI mass spectrometric methods. Altogether six crystal structures of complexes were determined to study the complexation in the solid state. Hydrogen bonding was observed to be the most important interaction for the complexation both in solution and in the solid state but – interactions also contribute to it. All crystal structures of the DB18C6 complexes with six-membered N-heteroaromatic cations, except for 4-hydroxypyridinium, are isomorphous to previously studied five-membered N-heteroaromatic cations and pyridinium complexes. Such a close resemblance is not observed in B18C6 and 18C6 complexes or DB18C6purinium (6).     

Mono- and dibridged isomers of Si2H3 and Si2H4: the true ground state global minima. Theory and experiment in concert

Highly correlated ab initio coupled-cluster theories (e.g., CCSD(T), CCSDT) were applied on the ground electronic states of Si(2)H(3) and Si(2)H(4), with substantive basis sets. A total of 10 isomers, which include mono- and dibridged structures, were investigated. Scalar relativistic corrections and zero-point vibrational energy corrections were included to predict reliable energetics. For Si(2)H(3), we predict an unanticipated monobridged H(2)Si-H-Si-like structure (C(s), (2)A') to be the lowest energy isomer, in constrast to previous studies which concluded that either H(3)Si-Si (C(s), (2)A') or near-planar H(2)Si-SiH (C(1), (2)A) is the global minimum. Our results confirm that the disilene isomer, H(2)Si-SiH(2), is the lowest energy isomer for Si(2)H(4) and that it has a trans-bent structure (C(2)(h), (1)A(g)). In addition to the much studied silylsilylene, H(3)Si-SiH, we also find that a new monobridged isomer H(2)Si-H-SiH (C(1), (1)A, designated 2c) is a minimum on the potential energy surface and that it has comparable stability; both isomers are predicted to lie about 7 kcal/mol above disilene. By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, the rotational spectrum of this novel Si(2)H(4) isomer has recently been measured in the laboratory, as has that of the planar H(2)Si-SiH radical. Harmonic vibrational frequencies as well as infrared intensities of all 10 isomers were determined at the cc-pVTZ CCSD(T) level.