Electrochemical fluorination of acetamide and formamide in a molten KH2F3

The electrofluorination of acetamide (CH₃CONH₂) and formamide (HCONH₂) on the anode was studied in a molten KH₂F₃ at 120°C. Amorphous carbon was used as the anode and Pt rod as the reference electrode. Anodic products were analyzed by both gas chromatography and infrared spectroscopy.In the both CH₃CONH₂ and HCONH₂, the anode effect did not occur in the current density range of 3-11mA²cm² and anode gas was then composed of N₂(+O₂), NF₃, CF₄, C₂F₆, N₂O, CO₂(+COF₂) and so on. The addition of 1.0w% LIF to the electrolyte was available for prevention from the anode effect.From these results, it is suggested that CH₃CONH₂ and HCONH₂ would react chemically with fluorine radical produced by the discharge of fluoride ion and that the change of the C_mF_n [(CF)_n?I] film on the anode to (CF)_n [(CF)_n?II] film was prevented specially in the case of HCONH₂. The mechanism of electrofluorination of CH₃CONH₂ in the melt is as folIows; CH₃CONH₂

CH₃COF,·NH₂

N₂,NF₃,CF₄,C₂F₆,CHF₃,COF₂(CO₂),N₂O.     

Intercalation of gaseous thiols and sulfides into Ag+ ion-exchanged aluminum dihydrogen triphosphate

Ag(+) ion-exchanged layered aluminum dihydrogen triphosphate (AlP) with the interlayer distance of 0.85 nm was synthesized by the ion-exchange of proton in triphosphate with Ag(+) ion. The amount of exchanged Ag(+) ion depended on the concentration of AgNO(3) aqueous solution. Ag(+) ion-exchanged AlP adsorbed gaseous thiols and sulfides into the interlayer region. The adsorption amounts of thiols were more than those of sulfides, thiols with one mercapto group > thiol with two mercapto groups > sulfides, and depended on the amount of exchanged Ag(+) ion in the interlayer region. The thiols with one mercapto group were intercalated to expand the interlayer distance of Ag(+) ion-exchanged AlP, whereas there was no expansion in the adsorption of sulfide. In the case of thiol with two mercapto groups, there was observed contraction of the interlayer distance through the bridging with Ag(+) ions of the upper and lower sides of the interlayer region.     

CO(2) as a separation switch for ionic liquid/organic mixtures

A novel technique to separate ionic liquids from organic compounds is introduced which uses carbon dioxide to induce the formation of an ionic liquid-rich phase and an organic-rich liquid phase in mixtures of methanol and 3-butyl-1-methyl-imidazolium hexafluorophosphate ([C4mim][PF6]). If the temperature is above the critical temperature of CO2 then the methanol-rich phase can become completely miscible with the CO2-rich phase, and this new phase is completely ionic liquid-free. Since CO2 is nonpolar, it is not equipped to solvate ions. As the CO2 dissolves in the methanol/[C4mim][PF6] mixture, the solvent power of the CO2-expanded liquid is significantly reduced, inducing the formation of the second liquid phase that is rich in ionic liquid. This presents a new way to recover products from ionic liquid mixtures and purify organic phases that have been contaminated with ionic liquid. Moreover, these results have important implications for reactions done in CO2/ionic liquid biphasic mixtures.     

Optimization of operating conditions of axially and radially viewed plasmas for the determination of trace element concentrations from ultrasound-assisted digests of soil samples contaminated by lead pellets

The method of ultrasound-assisted extraction followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of trace element concentrations (arsenic, copper, lead, antimony, and zinc) in shooting range areas was optimized. Optimization was achieved not only on the basis of the analysis of appropriate standard reference materials but also on that of 31 synthetic mixtures of matrix and analyte elements (aluminum, antimony, arsenic, calcium, copper, lead, iron, manganese, silicon, and zinc), in five concentrations. All the measurements were performed in robust plasma conditions which were tested by measuring the Mg II 280.270 nm/Mg I 285.213 nm line intensity ratio. The highest Mg II 280.270 nm/Mg I 285.213 nm line intensity ratios were observed when a nebulizer gas flow of 0.8 L min⁻¹, auxiliary gas flow of 0.2 L min⁻¹ and plasma power of 1400 W were used for both the axially and radially viewed plasmas. The analysis of 31 synthetic mixtures of the selected elements showed that As concentrations could be accurately determined with axially viewed plasma alone. The determination of Pb and Sb could be performed with either axially or radially viewed plasma whereas, surprisingly, Cu could be determined with high accuracy using radial plasma alone with a power of 1400 W. All the elements investigated were determined with high accuracy using robust plasma conditions and a combination of axially and radially viewed plasmas. The total recoveries of elements from SRM 2710 (Montana soil) and SRM 2782 (Industrial sludge) were highly comparable to leach recoveries certified by the National Institute of Standards and Technology (NIST).     

Synthesis of isocorrole and the higher homologues

Bis(azafulvene) derivative of gem-dimethyldipyrrylmethane reacted with 2,2′-bipyrrole under neutral conditions without catalyst to give a mixture of expanded isocorroles in ca. 50% total yields. GPC separation gave eleven porphyrinoids containing 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, and 44 units of pyrrole.     

Studies on antibacterial agents. III. Synthesis and antibacterial activities of substituted 1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acids

A series of substituted 4-oxoquinoline-3-carboxylic acids having a methyl group at the 8-position was prepared and tested for their antibacterial activity. 7-(trans-3-Amino-4-methyl-1-pyrrolidinyl)-1-cyclopropyl-1,4-dihydro-6- fluoro-8-methyl-4-oxoquinoline-3-carboxylic acid (21) exhibited highly potent antibacterial activity against both gram-positive and gram-negative bacteria, including Pseudomonas aeruginosa.     

Effects of Motion, Implied Direction and Displacement of a Large-Visual-Stimulus on Postural Control

Effects of motion, implied direction in a static stimulus and displacement on postural control were examined independently. In Experiment 1, rotation of a random-dot stimulus was presented. In Experiments 2 and 3, photographic slides of natural scenes were used; participants closed their eyes during stimulus rotation to eliminate motion information. In Experiment 2, the stimulus was presented upright initially, then presented again with a tilt. In Experiment 3, the order was reversed to separate the effects of implied direction and displacement. Results showed that all information of motion, implied direction, and displacement had some effect on postural control, although visual information of motion has been presumed to have a principal effect on postural control. Results suggested that the effects of implied direction might reflect an immediate processing of information. The effects of displacement and motion might reflect a continuous processing of information.