Fluorescence control of boron enaminoketonate using a rotaxane shuttle.

The effect of rotaxane shuttling on the fluorescence properties of a fluorophore was investigated by exploiting fluorophore-tethered [2]rotaxanes. A fluorescent boron enaminoketonate (BEK) moiety was introduced in a rotaxane via transformation of an isoxazole unit generated as a result of an end-capping reaction using a nitrile N-oxide. The rotaxane exhibited a red shift of the fluorescence maximum along with a remarkable enhancement of the fluorescence quantum yield through wheel translation to the fluorophore.

Click annulation of pseudo[2]rotaxane to [2]catenane exploiting homoditopic nitrile N-oxide.

A mild annulation reaction of a propargyl-terminated pseudorotaxane with a homoditopic stable nitrile N-oxide enabled the efficient synthesis of catenanes consisting of not only dibenzo-24-crown-8-ether (DB24C8) but also dibenzo-30-crown-10-ether (DB30C10) as a wheel component. A dynamic (1)H NMR study showed the highly enhanced mobility of the components of the DB30C10-based [2]catenane due to the enlarged wheel cavity.

C-C bond-forming click synthesis of rotaxanes exploiting nitrile N-oxide.

A click end-capping reaction exploiting nitrile N-oxide to rotaxane was described with emphasis of productivity of the protocol via stable C-C bond formation. Establishment of a pH-driven molecular shuttling system was also demonstrated by practical neutralization of the sec-ammonium group of the rotaxane axle with potassium hydroxide.

Determination of dioxins and polychlorinated biphenyls in breast milk, maternal blood and cord blood from residents of Tohoku, Japan.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are bioaccumulative chemicals that are considered to be toxic contaminants based on several epidemiological studies. To elucidate exposure levels of these chemicals in the present study, concentrations of PCDD/DFs, dioxin-like PCBs (DL-PCBs) and PCBs in breast milk, maternal blood and cord blood obtained from the same participants registered in a birth cohort study in Tohoku, Japan, were measured. Congener-specific analysis revealed several differences in minor congeners of these compounds among the three specimen types, although major congeners were detected in the specimens. The toxicity equivalence quantity concentrations (1998 WHO-TEF) and PCBs in breast milk, maternal blood and cord blood on the whole and on a lipid basis were in the order of breast milk > maternal blood > cord blood. Pearson's correlation coefficients of TEQs and total PCBs among the three specimens were high, with the correlation coefficient of TEQ between breast milk and maternal blood being the highest (r=0.94, p<0.001). On the other hand, the TEQ between breast milk and cord blood was the lowest (r=0.79, p<0.001). Pearson's correlation coefficient between the TEQ and PCBs in each specimen was also high (r=0.82-0.95, p<0.001). The associations of chemical concentrations with maternal age, parity, fish intake, BMI and the rate of body weight increase during pregnancy were analyzed with multiple linear regression analysis. TEQ concentrations and PCBs were negatively associated with parity (p<0.05), and maternal age was positively associated with PCBs (p<0.05). However, the associations with BMI and fish intake during pregnancy were not significant. These results suggest that parity is an important factor affecting the concentrations of dioxins and PCBs in these specimens.

Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry.

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.

Removal efficiency and homologue patterns of dioxins in drinking water treatment.

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) analyses in raw and treated water throughout Japan were implemented to identify the concentration and homologue patterns of dioxins before and after the water treatment process. In 40 surface water and 5 ground water treatment plants, the removal efficiency of dioxins and the influence of extent chlorination on dioxins increase in drinking water were also studied. Raw water and treated water were sampled twice, summer and winter. The mean concentration in raw water and treated water of dioxins was 56.45 pg/L (0.15 pg WHO-TEQ/L) and 4.24 pg/L (0.019 pg WHO-TEQ/L), respectively. Location of water treatment plants not only significantly influenced the concentration level of dioxins but also resulted in different homologue patterns of dioxins. Levels of dioxins in ground water were much less than that of surface water in both raw and treated water. This study shows most dioxin congeners are well removed (87% removal efficiency) by water treatment. However, in some water treatment plants, the level of TeCDFs (pg WHO-TEQ/L) increased as a result of chlorination.