Electrosynthesis and charge-transport properties of poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene)

Polythiophene containing 3,4-ethylenedioxythiophene (EDOT), poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene), was synthesized by electrochemical oxidation of the corresponding monomer, 3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene, in acetonitrile. The resulting polymer was soluble in DMSO and THF, and was characterized by ¹H NMR and mass spectroscopies, and GPC. The electrical conductivity of the oxidized polymer film was found to be comparable to those for polythiophene and poly(methylthiophene) despite of its short π-conjugation length.     

Mass balance and kinetic analysis of anaerobic microbial dechlorination of pentachlorophenol in a continuous flow column

A mass balance and kinetic investigation of anaerobic dechlorination of pentachlorophenol (PCP) was undertaken using an enriched microbial consortium in a laboratory scale continuous flow column, as a model microbial permeable reactive barrier. The chlorine balance showed that 50 µM PCP was largely dechlorinated to phenol with the formation of a small quantity of 3-chlorophenol as an intermediate metabolite (hydraulic retention time 7.6 days), and the chlorine removal efficiency reached 36 µM d^-1. When the initial PCP concentration was increased to 100 µM the chlorine removal efficiency increased 1.5 times. However, the dechlorination activity disappeared after 7.4 pore volumes (58 days), demonstrating the susceptibility of the dechlorination culture to high concentrations of PCP. Lactate released hydrogen as an electron donor during PCP dechlorination, with acetate, propionate, CO₂ and CH₄ as byproducts. The carbon balance showed that some of the organic carbon source (PCP, lactate) in the influent was converted to gas and utilized for biomass growth in addition to organic metabolites. The kinetic study was conducted in a batch culture and yielded 1.99 mg l^-1 biomass growth per unit of chlorine consumption (µM). The Monod equation was well fitted to the specific growth rate of 1.38 d^-1 and a half saturation constant of 0.29 µM. The organic chlorine removal rate in the batch culture was consistent with the results in the flow column, indicating the feasibility of and potential for in situ estimation and prediction through batch culture studies.     

Spray-dry synthesis of β-Cu1.8Zn0.2V2O7 ceramic fine particles showing giant negative thermal expansion

We used spray-dry method to synthesize fine powder of β-Cu_1.8Zn_0.2V₂O₇ showing large negative thermal expansion (NTE) linearly to temperature over a wide temperature range. The NTE of β-Cu_1.8Zn_0.2V₂O₇ is produced by microstructures consisting of voids and anisotropic thermal deformation of crystal grains in ceramics. By reducing the size of the microstructures that produce NTE, large NTE equivalent to that of bulk was realized, even for ceramic particles of about 2 μm size. Comparison with particles produced using a conventional method demonstrates that the particle size distribution is narrow and that the particles are nearly spherical. This achievement is expected to pave the way to use of NTE materials in micrometer-scale control of thermal expansion.     

Melatonin-Induced Postconditioning Suppresses NMDA Receptor through Opening of the Mitochondrial Permeability Transition Pore via Melatonin Receptor in Mouse Neurons

Mitochondrial membrane potential regulation through the mitochondrial permeability transition pore (mPTP) is reportedly involved in the ischemic postconditioning (PostC) phenomenon. Melatonin is an endogenous hormone that regulates circadian rhythms. Its neuroprotective effects via mitochondrial melatonin receptors (MTs) have recently attracted attention. However, details of the neuroprotective mechanisms associated with PostC have not been clarified. Using hippocampal CA1 pyramidal cells from C57BL mice, we studied the involvement of MTs and the mPTP in melatonin-induced PostC mechanisms similar to those of ischemic PostC. We measured changes in spontaneous excitatory postsynaptic currents (sEPSCs), intracellular calcium concentration, mitochondrial membrane potential, and N-methyl-D-aspartate receptor (NMDAR) currents after ischemic challenge, using the whole-cell patch-clamp technique. Melatonin significantly suppressed increases in sEPSCs and intracellular calcium concentrations. The NMDAR currents were significantly suppressed by melatonin and the MT agonist, ramelteon. However, this suppressive effect was abolished by the mPTP inhibitor, cyclosporine A, and the MT antagonist, luzindole. Furthermore, both melatonin and ramelteon potentiated depolarization of mitochondrial membrane potentials, and luzindole suppressed depolarization of mitochondrial membrane potentials. This study suggests that melatonin-induced PostC via MTs suppressed the NMDAR that was induced by partial depolarization of mitochondrial membrane potential by opening the mPTP, reducing excessive release of glutamate and inducing neuroprotection against ischemia-reperfusion injury.     

Polyphasic characterization of two microbial consortia with wide dechlorination spectra for chlorophenols

Two soil-free anaerobic dechlorinating cultures (3-CP and 35-DCP) were enriched from a pentachlorophenol (PCP)-to-phenol dechlorinating soil-dependent culture, using 3-chlorophenol (3-CP) and 3,5-dichlorophenol (3,5-DCP) as specific respective substrates, and characterized polyphasically. Physiological characterization indicated that the 3-CP and 35-DCP cultures had similar features, but with some variations. Both cultures utilized formate or acetate preferably as optimum electron donors for reductive dechlorination, and they shared similar patterns of dechlorination spectra for chlorophenols ranging from mono-CPs to a tetra-CP, with preferred dechlorination pathways in the ortho and meta positions. Alternative electron acceptors such as NO(3)(-) but not SO(4)(2-) inhibited the dechlorination activity in both cultures, while amorphous iron oxides (FeOOH) suppressed dechlorination activity only in the 35-DCP culture. Complete inhibition of dechlorination was observed in both cultures supplemented with chloramphenicol and vancomycin. The addition of 2-bromoethanesulfonate resulted in delayed dechlorination activity in the 35-DCP culture but not in the 3-CP culture; molybdate did not exert any inhibitory effect in either culture. Phylogenetic analysis based on 16S rRNA genes confirmed that the two cultures exhibited similar bacterial species but with varied responsible dechlorinators. Dehalobacter spp. were the likely dechlorinators in the 3-CP culture versus Sulfurospirillum spp. in the 35-DCP culture, with Clostridium and Clostridium-like spp. as candidate dechlorinators in both cultures.     

Synergistic Extraction of Am(III) and Eu(III) by Tris(2‐pyridylmethyl)Amine with Various Anions in 1,2‐Dichloroethane

The extraction equilibria of Am(III) and Eu(III) by using a tripodal ligand, tris(2‐pyridylmethyl)amine (tpa), with various lipophilic anions have been investigated. The extractability of both Am(III) and Eu(III) was increased by the combination of tpa and counteranions due to a synergistic effect. The separation factors between Am(III) and Eu(III) were also increased from 7.6 to 49 by the combination of counteranions and organic solvents. The extraction equilibria of Am(III) and Eu(III) with tpa in 1,2‐dichloroethane were determined by slope analysis. It was found that three anions and one molecule of the ligand coordinated to Am(III) and Eu(III) was extracted regardless of the anions.     

Lubrication Mechanism of Phosphonium Phosphate Ionic Liquid Additive in Alkylborane–Imidazole Complexes

The assessment of ionic liquids (ILs) as lubricants in several tribological systems has shown their ability to provide remarkable reduced friction and protection against wear, whether they are used as additives or in the neat form. However, their corrosion and limited solubility in non-polar hydrocarbon oils represent the bottleneck-limiting factors for the use of ILs as lubricants. Therefore, in order to tackle these problems, mixtures of alkylborane–imidazole complexes with one halogen-free IL as additive were used in this study. The knowledge of the additive–surface interactions and hence the understanding of tribological properties are an important issue for lubricant formulations and were also investigated in this work. Thus, combination effects between two ionic liquid additives, a halogenated and a halogen-free one, were evaluated by a ball-on-disc-type tribometer under boundary lubrication conditions. Effective friction reduction and anti-wear properties have been demonstrated in tribological investigations when adding between 0.7 and 3.4 wt% of the halogen-free IL into base fluid composed of alkylborane–imidazole complexes. X-ray photoelectron spectroscopy analyses of the steel specimens were conducted to study the correlation between tribological properties and chemical surface composition of the boundary films formed on the rubbing surface. This work suggests potential applications for using halogen-free ILs as additives for synthetic ionic liquid lubricants.     

Thermophysical properties of (U,Y)O2

We prepared polycrystalline pellets of (U,Y)O₂, containing YO_1.5 up to 11 mol.%. We performed indentation tests on the pellets, and evaluated the Young’s modulus and hardness. We measured the heat capacity and the thermal diffusivity, and evaluated the thermal conductivity. We succeeded in evaluating the effect of Y content on the thermophysical properties of (U,Y)O₂. We revealed that the Young’s modulus, hardness, and thermal conductivity of (U,Y)O₂ decreased with increasing the Y content.