PCDD/DF and co-planar PCB emissions from crematories in Japan.

Japan implemented dioxin emission guidelines for crematories in 2000, but the effects of the new guidelines have not been fully evaluated. In this study, concentrations of polychlorinated dibenzodioxins/dibenzofurans (PCDDs/DFs) and co-planar polychlorinated biphenyls (co-PCBs) were measured in flue gas, fly ash, and bottom ash (mainly bone) from several crematories as a follow-up investigation. Total concentrations (O2 12% normalized) of PCDDs/DFs and co-PCBs in flue gas ranged from 4.2 to 540 ng/mN(3), and toxic equivalent concentrations ranged from 0.000053 to 11 ng-TEQ/mN(3). Based on these measurements, the average emission factor was estimated to be 1400 ng-TEQ/body. This is approximately one-third the emission factor recorded in 1999. The emission factor distributions from 1999 and our study in 2007 were log-normally distributed. Emission factors were significantly lower in 2007 than in 1999, which suggests that the guidelines have been effective in reducing dioxin emissions. Meanwhile, toxic equivalent concentrations in fly ash ranged from 0.014 to 13 ng-TEQ g(-1). Higher dioxin concentrations in fly ash were observed in facilities that used a heat exchanger as a flue-gas cooling device. Because the concentrations of PCDDs/DFs and co-PCBs in flue gas were also elevated after heat exchangers during the investigation of PCDD/DF- and co-PCB-removal behaviors, secondary formation of PCDDs/DFs and co-PCBs on heat exchanger surfaces unambiguously occurred.

Advantage of vein grafts for anomalous origin of a right coronary artery.

A 66-year-old man with anomalous origin of the right coronary artery suffered from chest pain. The results of coronary angiography and multidetector computer tomography indicated that the proximal right coronary artery was intermittently compressed, causing the ischemia. Coronary artery bypass grafting was regarded as a reliable treatment compared with percutaneous coronary intervention or other surgeries. Because of plentiful flow of the right coronary artery, we decided to use a vein graft to avoid competitive flow. Postoperative coronary angiography revealed intact flow in both the native coronary artery and the vein graft 1 year after the surgery. The myocardial ischemia seen on scintigraphy and the chest pain had disappeared.

Risk factors for severe coronary artery disease - a case-control study of patients who have undergone coronary artery bypass grafting.

To investigate risk factors for coronary artery disease (CAD), we analyzed the clinical parameters of patients with a coronary artery bypass graft (CABG) in a case-control study. Eighty-eight patients (75 males and 13 females) who underwent CABG surgery between 2001 and 2002 were compared with age- and sex-matched healthy controls randomly chosen from the registry of Kobari Health Care Center. Wilcoxon's signed rank test and McNemar's test were used for pairwise comparisons. Multivariate logistic regression analysis was used to identify significant risk factors for CABG. Significant differences between the patients and controls were observed in HDL-C (p < 0.001), HbA(1c) (p < 0.001), Brinkman Index (BI; p < 0.001), body mass index (BMI; p = 0.002), and systolic blood pressure (SBP; p = 0.013). Subjects with an abnormal BMI, HbA(1c), or HDL-C or high BI value made up a significantly higher proportion of the patients who underwent CABG, compared to their age- and sex-matched controls. Multivariate logistic regression analysis identified high levels of HbA(1c), low levels of HDL-C, and high scores on the BI as significant risk factors for needing a CABG. These results demonstrate that, despite the modification of laboratory determinations by antecedent treatment, HDL-C, HbA(1c), BI, BMI, and SBP are significant indicators of risk for CAD.

Ring Expansion of Diazo-Functionalized 4-Hydroxycyclobutenone: Catalytic Ring Opening and Recyclization to 2(5H)-Furanone/Cyclopentenedione and Thermal 4pi-8pi Electrocyclic Ring Opening-Closure to Diazepinedione.

The acid-catalyzed and Rh-catalyzed (also photolyzed) decomposition of 4-hydroxycyclobutenones with a diazo group at C-4 gave 2(5H)-furanone and/or cyclopentene-1,3-dione via an alpha-carbocation intermediate and a carbenoid (carbene) intermediate, respectively. Thermal rearrangement of some of these compounds led to the formation of diazepinediones without the extrusion of nitrogen through tandem 4pi electrocyclic ring opening and 8pi electrocyclic ring closure processes.

Cyclization of Hindered Fluorinated Dichloro(5- and 6-)alkenyl Radicals. Structural Effects of Olefins on the Selective Formation of 5-exo and 6-endo Cyclization Products.

Reaction of 3-butenyl radicals generated by photolysis of variously substituted Barton esters (both open-chain 1a-d and cyclohexyl 1e-h) with CF(2)=CCl(2) gave a mixture of cyclized products (cyclopentanes 6 and 8 and cyclohexanes 7 and 9) as well as noncyclized products (4and 5) in various ratios depending on the substitution pattern at the olefinic moiety. The product ratios of [cyclization (6 + 7 + 8 + 9):noncyclization (5)] for 1 with more alkyl substituents on the CC double bond were greater than those for 1 with fewer substituents. The products ratio of [5-exo (6 + 8):6-endo (7 + 9)] was influenced by a steric effect. Photoreaction of Barton ester 2 with CF(2)=CCl(2) gave a mixture of cyclohexanes 16 and 17 as well as noncyclized 14 and 15. Dehydrochlorination of decalins 7g and 7h followed by oxidation of sulfide and [2,3]sigmatropic rearrangement of the allyl sulfoxide gave octahydronaphthalenones 23 and 27, respectively.

Generation of 6-(Trifluoromethyl)-4,5-dihydro-2(3H)-pyridone and the Application to Synthesis of Some Fused Nitrogen Heterocycles Carrying a Trifluoromethyl Group on the Bridgehead Position via Radical Cyclization of Dihydropyridones.

Staudinger/aza-Wittig reaction of 6,6,6-trifluoro-5-oxohexanoyl azide with PPh(3) or PBu(3) was examined. A reactive intermediate acyl imine 1 was trapped by methanol. Without nucleophile, isomerized enamide form 3 was obtained. N-Iodobenzoylation and N-haloalkylation of 3 and following radical cyclization via the 5-exo or 6-exo mode gave benzoindolizidinone, indolizidinone, and quinolizidinone derivatives 10-14, which have a trifluoromethyl group at the bridgehead position adjacent to nitrogen. Although LiAlH(4) reduction of 10 and 11 gave a mixture of saturated benzoindolizidine 15 and amino alcohol 16, reduction with BH(3)/THF selectively gave the desired 15 and indolizidine 17 from 13.

Synthesis of Optically Active Vasicinone Based on Intramolecular Aza-Wittig Reaction and Asymmetric Oxidation(1).

Both optical isomers of a quinazoline alkaloid, vasicinone, were synthesized by two different methods. The first method used (3S)-3-hydroxy-gamma-lactam as a chiral synthon, which was, after O-TBDMS protection, o-azidobenzoylated followed by treatment with tri-n-butylphosphine to afford (S)-(-)-vasicinone via the tandem Staudinger/intramolecualr aza-Wittig reaction. The second method utilized asymmetric oxygenation of deoxyvasicinone with (1S)-(+)- or (1R)-(-)-(10-camphorsulfonyl)oxaziridine (the Davis reagent), respectively. The aza-enolate anion of deoxyvasicinone was treated with (S)-(+)-reagent to afford (R)-(+)-vasicinone in 71% ee, while the reaction with (R)-(-)-reagent gave (S)-(-)-vasicinone in 62% ee. The optical purity was analyzed by HPLC on specially modified cellulose as a stationary phase. These results provided a facile method to prepare both optical isomers of vasicinone and confirmed the recently reversed stereochemistry of natural (-)-vasicinone.