Aryl-aryl coupling reaction using a novel and highly active palladium reagent prepared from Pd(OAc)2, 1,3-bis[diphenylphosphino]propane (DPPP), and Bu3P

A palladium-assisted coupling reaction of aryl triflate with arene was investigated, and a novel Pd reagent prepared from equimolar Pd(OAc)2, 1,3-Bis[diphenylphosphino]propane (DPPP), and Bu3P was developed. This method is useful for intramolecular biaryl coupling reactions, not only between aryl triflate and arene (triflate-amide), but also between aryl halide and arene (halo-amide).     

NMR and MO Studies on the Molecular Structure of a Fluoranthene-Benzene Complex

Summary. Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The ¹H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the ¹H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of C_S symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the ¹H NMR spectral shifts mentioned above and the experimentally predicted C_S structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure.     

Stabilization of enhanced chirality from pyrene-containing l-glutamide lipid in methyl methacrylate by photo-induced polymerization

Enhanced CD spectra based on chirally-oriented structures of pyrene-containing L-glutamic acid-derived lipid were observed in polymerizable monomers and CD strength was maintained after photo-induced polymerization of the monomer solvents.     

Bitterness evaluation of medicines for pediatric use by a taste sensor

The purpose of this study was to evaluate the bitterness of 18 different antibiotic and antiviral drug formulations, widely used to treat infectious diseases in children and infants, in human gustatory sensation tests and using an artificial taste sensor. Seven of the formulations were found to have a bitterness intensity exceeding 1.0 in gustatory sensation tests (evaluated against quinine as a standard) and were therefore assumed to have an unpleasant taste to children. The bitterness intensity scores of the medicines were examined using suspensions in water or an acidic sports drink. In the case of three macrolide antibiotic formulations containing erythromycin (ERYTHROCIN dry syrup), clarithromycin (CLARITH dry syrup for pediatric), and azithromycin (ZITHROMAC fine granules for pediatric use), the bitterness intensities of suspensions in acidic sports drinks were dramatically enhanced compared with the corresponding scores of suspensions in water. This enhancement could be predicted using the taste sensor. On the other hand, a reduction of bitterness intensity was observed for an acidic sports drink suspension of an amantadine product (SYMMETREL fine granules) compared with an aqueous suspension. This reduction in bitterness could also be predicted using the taste sensor output value. Thus, the taste sensor could predict whether or not suspension in an acidic sports drink would enhance or reduce the bitterness intensity of pediatric drug formulations, compared with suspensions in water.     

Carbon dioxide fixation by microalgae photosynthesis using actual flue gas discharged from a boiler

To mitigate CO₂ discharged from thermal power plants, studies on CO₂ fixation by the photosynthesis of microalgae using actual exhaust gas have been carried out. The results are as follows.

Analysis of the mechanism of retention on graphitic carbon by a computational chemical method

Retention mechanism on a graphitic carbon was analyzed by computational chemical calculation. The model graphitic carbon phase was a large polycyclic aromatic hydrocarbon (PAH) and analytes were carbohydrates and hydrocarbons separated by liquid and gas chromatography. Molecular mechanics calculation was fast and suggested their retention order and main retention force. Molecular orbital package calculation (MOPAC) demonstrated their complex form.     

Electroreductive intramolecular coupling of aliphatic cyclic imides with ketones and O-methyloximes

The electroreductive intramolecular coupling of aliphatic cyclic imides with ketones in isopropanol gave five- and six-membered cyclized products. Similarly, the electroreductive intramolecular coupling of aliphatic cyclic imides with O-methyloximes afforded five-, six-, and seven-membered cyclized products. These reactions provide a useful method to synthesize azabicyclo[n.m.0] compounds. The bicyclic products were stereoselectively transformed to the corresponding deoxylated compounds by reduction with NaB(CN)H₃ or Et₃SiH/BF₃·Et₂O.     

Swallow-tailed perylene derivative: a new tool for fluorescent imaging of lipid hydroperoxides

A swallow-tailed perylene derivative including a triphenylphosphine moiety was synthesized and applied to the detection and the live-cell imaging of lipid hydroperoxides. The novel probe, named Spy-LHP, reacted rapidly and quantitatively with lipid hydroperoxides to form the corresponding oxide, Spy-LHPOx, which emits extremely strong fluorescence (Phi approximately 1) in the visible range (lambda(em) = 535 nm, 574 nm). Spy-LHP was highly selective for lipid hydroperoxides, and the addition of other reactive oxygen species (ROS) including hydrogen peroxides, hydroxyl radical, superoxide anion, nitric oxide, peroxynitrite, and alkylperoxyl radical, caused no significant increase in the fluorescence intensity. The probe exhibited good localization to cellular membranes and was successfully applied to the confocal laser scanning microscopy (CLSM) imaging of lipid hydroperoxides in live J774A.1 cells, in which lipid peroxidation was proceeded by the stimulation of 2,2-azobis(2-amidinopropane)dihydrochloride (AAPH). These findings establish Spy-LHP as a promising new tool for investigating the physiology of lipid hydroperoxides.     

A fluorescent photochromic compound for labeling biomolecules

A fluorescent photochromic compound, composed of diarylethene, fluorescein and succinimidyl ester units, was developed for the controllable fluorescent labeling of biomolecules based on a small molecule.