Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

Polymer electrolytes containing N,N′-(trans-cyclohexane-1,4-diyl)dibenzamide linkages, polyethylene ((CH₂)_m, m = 2, 4, 10) spacers, and bis(trifluoromethanesulfonyl)amide (TFSA) or bis(fluorosulfonyl)amide (FSA) counteranions (polymer abbreviation: CDBAm•X; m = 2, 4, 10; X = TFSA, FSA) have been synthesized, adding to our previous report (m = 6). In addition, their ability to effect the gelation of six ionic liquids and the properties of the resulting ionogels have been examined. The polymers, except for CDBA10•TFSA, effect the gelation for all ionic liquids used in this study at fairly low concentrations (0.9–50 g/L). Ionogel ionic conductivity is not dependent on the spacer length, but does decrease slightly as increasing amounts of the gelatinizer are introduced. In contrast to ionic conductivity, the temperatures at which these ionogels transition into isotropic fluids is dependent on the spacer length; the gel composed of [EMI][FSA] and 100 g/L of CDBA6•FSA transforms at 120 °C, while the gel composed of [EMI][FSA] and 5 g/L of CDBA2•FSA does not transform into a sol even when temperatures become 155 °C. In brief, ionogel heat resistance can be improved by changing the spacer length of the polyelectrolyte. Finally, it has been determined using cyclic voltammetry that the potential window of the polyelectrolytes is particularly wide, ranging from −1.6 to 2.5 V. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 249–255     

Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species

The structure of FeO_x species supported on γ‐Al₂O₃ was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al₂O₃ and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe₂O₃ particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al₂O₃ surface.     

Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem

Penitrem A is one of the most elaborated members of the fungal indole diterpenes. Two separate penitrem gene clusters were identified using genomic and RNA sequencing data, and 13 out of 17 transformations in the penitrem biosynthesis were elucidated by heterologous reconstitution of the relevant genes. These reactions involve 1) a prenylation‐initiated cationic cyclization to install the bicyclo[3.2.0]heptane skeleton (PtmE), 2) a two‐step P450‐catalyzed oxidative processes forming the unique tricyclic penitrem skeleton (PtmK and PtmU), and 3) five sequential oxidative transformations (PtmKULNJ). Importantly, without conventional gene disruption, reconstitution of the biosynthetic machinery provided sufficient data to determine the pathway. It was thus demonstrated that the Aspergillus oryzae reconstitution system is a powerful method for studying the biosynthesis of complex natural products.     

Effect of Static Magnetic Field on Photocatalytic Degradation of Methylene Blue over ZnO and TiO2 Powders

Magnetic field effects (MFEs) on photocatalytic degradation of methylene blue (MB) solution over ZnO and TiO₂ powders are investigated under static magnetic field up to 0.7 T with light irradiation by ultraviolet (UV) light emitting diode. The UV–visible-near-infrared spectrometer is used to monitor the MB concentrations. The positive MFE is observed for ZnO, while the negative MFE for TiO₂, and both MFEs are increased with the increase in the magnetic field applied. By increasing the settling time (the time interval between the preparation of MB solution and the powder dispersion into the MB solution), the photodegradation abilities under MFEs are decreased for both the catalysts. The cause of MFE is discussed in terms of dissolved oxygen in the MB solution and magnetic adsorption of the constituent molecules.     

Morphological studies of a hydrogen-bonded LC polymer obtained by photopolymerization in LC solvents

Anisotropic morphologies and the phase behaviour of a hydrogen-bonded LC polymer obtained by photopolymerization in two kinds of LC solvent are discussed. The hydrogen-bonded LC monomer, 4-(6-acryloyloxyhexyloxy) benzoic acid (A6OBA), was photopolymerized in 4-cyano-4′-hexyloxybiphenyl (6OCB) and in 4-cyano-4′-undecyloxybiphenyl (11OCB), which show a nematic phase and a smectic A phase, respectively. After photo-polymerization, the LC media were removed by extraction and the pure polymer was observed by scanning electron microscopy. SEM images showed that the polymer possessed fibrous morphology with a fibre diameter of a few micrometers, based on polymerization-induced phase separation. The overall geometries reflected typical LC characteristics such as schlieren and focal-conic fan textures. It was found that the hydrogen bond between benzoic acid groups in the monomer was rigid enough to fix the anisotropic phase-separated structure forming during the early stage of phase separation; however, it could not permanently maintain the fibre structure due to dissociation at elevated temperature. X-ray measurements revealed that a well developed layer structure of the hydrogen-bonded mesogen existed in the polymer obtained from the smectic phase of 11OCB, whereas a polymer layer structure could develop only partially from the nematic phase of 6OCB.     

Structures and Reaction Mechanism of Novel Metal-Carbene Complexes Derived from Hypervalent Diazadiselenathiapentalenes

Abstract

Novel metal-carbene complexes (4) with a metallapentalene framework have been obtained from hypervalent diazadiselenathiapentalenes (3) by treating with Pt(PPh₃)₄, Pd(PPh₃)₄ and RhCl(PPh₃)₃. X-Ray investigations revealed that the central hypervalent sulfur atom in 3 was substituted by a metal atom to form M-Se bonds in the resultant metallapentalene framework.     

Phase behavior of binary mixtures composed of ethylene carbonate and various organic solvents

Phase behaviors of the binary mixtures composed of ethylene carbonate (EC) and aliphatic alcohols, ω-phenyl alcohols, and alkylbenzenes were investigated. In addition, heat of solution of EC into these organic solvents was measured. The EC/methanol and EC/ethanol systems gave homogeneous solution at the temperature above their liquidus lines, while the mixtures of EC and alcohols with longer alkyl chain showed a miscibility gap in a liquid phase and provided the monotectic-type phase diagram. The liquid–liquid phase separation region expanded with the increase in the alkyl chain length. A similar phase behavior was also observed for the mixtures of EC and alkylbenzenes. On the other hand, the EC mixtures with ω-phenyl alcohols showed no miscibility gap in a liquid phase at least up to 4-phenylbutan-1-ol which has C4 alkyl chain intervening between phenyl and hydroxyl groups. This result demonstrates that both of the hydroxyl and phenyl groups act to facilitate the mixing of aliphatic compounds with EC. The phase behavior of these EC mixtures was analyzed applying the modified regular solution model in which the pair interaction energy was regarded as free energy. The model calculation with the use of heat of solution of EC at infinite dilution as the pair interaction enthalpy reproduced well both of the experimentally obtained liquidus line and mutual solubility curve as well as monotectic point.