Smiles-type free radical rearrangement of aromatic sulfonates and sulfonamides: syntheses of arylethanols and arylethylamines

Smiles-type free radical rearrangements of arenesulfonates and arenesulfonamides are exploited for synthetic purposes. 4-Substituted benzenesulfonates cause Smiles-type rearrangement only when substituted by an electron withdrawing group. Therefore, ipso-attack by an alkyl radical on arenesulfonates takes place in an electrophilic manner. Arenesulfonamides rearrange only when the amide nitrogen is substituted by an alkoxycarbonyl group, due to the electron withdrawing nature of this group. Sulfonates and the N-ethoxycarbonylsulfonamide derivatives of naphthalene, quinoline, and thiophene cause more rearrangement and show synthetic utility. Aromatic amino acid analogues were synthesized by Smiles-type rearrangement with moderate yields. The radical Smiles-type rearrangement of sulfonate and sulfonamide derivatives can be a useful synthetic route when we understand the electronic character of these reactions.     

Encapsulating property of ap-t-butylcalix[6]arene derivative: Formation of charge-transfer complexes of alkadienes with iodine in the presence of octopus-type calix[6]arene

This paper deals with the ability ofp-tert-butylcalix[6]arene derivative1, which has six 3,6,9-trioxadecyl substituents at the phenolic oxygens, to encapsulate CT complexes of alkadienes with iodine. By adding I₂ to alkadienes in CH₂Cl₂ in the presence of1, the absorbance at 363 nm, which was ascribed to I ₃ ^– ion, increased in the order: 1,5-hexadiene<1,9-decadiene 1,7-octadiene. The reactivity features of the CT complexes in the presence of1 are discussed.     

SO+(A2Π-X2Πr) emission produced from a dissociative charge-transfer reaction of He+ with SO2 at thermal energy

The extensive bands observed from the helium afterglow reaction of SO₂ in the 250–540 nm region are assigned to the new SO⁺(A²Π-X²Π_r) system produced from the He⁺/SO₂ dissociative charge-transfer reaction at thermal energy. They had been erroneously interpreted as the SO⁺₂ (C?-X?) system produced from He(2³S)/SO₂ Penning ionization. The spectroscopic constants for the SO⁺A²Π) and SO⁺(X²Π_r) states were determined.     

Internal radiocesium contamination of adults and children in Fukushima 7 to 20 months after the Fukushima NPP accident as measured by extensive whole-body-counter surveys

The Fukushima Dai-ichi NPP accident contaminated the soil of densely-populated regions in Fukushima Prefecture with radioactive cesium, which poses significant risks of internal and external exposure to the residents. If we apply the knowledge of post-Chernobyl accident studies, internal exposures in excess of a few mSv/y would be expected to be frequent in Fukushima.Extensive whole-body-counter surveys (n = 32,811) carried out at the Hirata Central Hospital between October, 2011 and November, 2012, however show that the internal exposure levels of residents are much lower than estimated. In particular, the first sampling-bias-free assessment of the internal exposure of children in the town of Miharu, Fukushima, shows that the ¹³⁷Cs body burdens of all children (n = 1,383, ages 6–15, covering 95% of children enrolled in town-operated schools) were below the detection limit of 300 Bq/body in the fall of 2012. These results are not conclusive for the prefecture as a whole, but are consistent with results obtained from other municipalities in the prefecture, and with prefectural data.     

Synthesis and Reactions of 1-Phenylbenzo[b]thiophenium Salts

1-Phenylbenzo[b]thiophenium salts are prepared and reacted under thermal and photochemical conditions. The chemical behaviors are discussed.     

Comparative investigation of Au nano-particle formation process dependent upon various protective agents

Formation process of gold nanoparticles was investigated by near-field heterodyne transient grating method. In the absence of the protective agents, although the diffusion of H[Au^ICl₂] could be observed after the photo-reduction of H[Au^IIICl₄], the diffusion of nanoparticle-seeds was not observed. On the other hand, in the presence of the protective agents, the diffusion of a complex molecule (Au and protective agent) and nanoparticle-seeds could be observed. From these results, it was found that enough amount of the complex is essential for the nanoparticle formation. We also investigated the formation process with four different chemicals as a protective agent. The hydrodynamic radius of nanoparticle-seeds generated in the poly(vinyl pyrrolidone) and TritonX-100 solutions were larger than those generated in the Tween 20 and Brij 58 solutions. The former two have hydrophilic chain in the molecular structure; on the other hand, the latter two have hydrophobic alkyl chain. Based on those facts, we concluded that the interaction between the chains of the complex molecule plays an important role in the nanoparticle formation process.     

Enhancing the Cellulose-Degrading Activity of Cellulolytic Bacteria CTL-6 (Clostridium thermocellum) by Co-Culture with Non-cellulolytic Bacteria W2-10 (Geobacillus sp.)

The effect of a non-cellulolytic bacterium W2-10 (Geobacillus sp.) on the cellulose-degrading activity of a cellulolytic bacterium CTL-6 (Clostridium thermocellum) was determined using cellulose materials (paper and straw) in peptone cellulose solution (PCS) medium under aerobic conditions. The results indicated that in the co-culture, addition of W2-10 resulted in a balanced medium pH, and may provide the required anaerobic environment for CTL-6. Overall, addition of W2-10 was beneficial to CTL-6 growth in the adverse environment of the PCS medium. In co-culture with W2-10, the CTL-6 cellulose degradation efficiency of filter paper and alkaline-treated wheat straw significantly increased up to 72.45 and 37.79 %, respectively. The CMCase activity and biomass of CTL-6 also increased from 0.23 U ml^?1 and 45.1 μg ml^?1 (DNA content) up to 0.47 U ml^?1 and 112.2 μg ml^?1, respectively. In addition, co-culture resulted in accumulation of acetate and propionate up to 4.26 and 2.76 mg ml^?1. This was a respective increase of 2.58 and 4.45 times, in comparison to the monoculture with CTL-6.