Measurement of Secondary Products During Oxidation Reactions of Terpenes and Ozone Based on the PTR-MS Analysis: Effects of Coexistent Carbonyl Compounds

Continuous measurements using proton transfer reaction mass spectrometry (PTR-MS) can be used to describe the production processes of secondary products during ozone induced oxidation of terpenes. Terpenes are emitted from woody building materials, and ozone is generated from ozone air purifiers and copy machines in indoor environments. Carbonyl compounds (CCs) are emitted by human activities such as smoking and drinking alcohol. Moreover, CCs are generated during ozone oxidation of terpenes. Therefore, coexistent CCs should affect the ozone oxidation. This study has focused on the measurement of secondary products during the ozone oxidation of terpenes based on the use of PTR-MS analysis and effects of coexistent CCs on oxidized products. Experiments were performed in a fluoroplastic bag containing α-pinene or limonene as terpenes, ozone and acetaldehyde or formaldehyde as coexistent CCs adjusted to predetermined concentrations. Continuous measurements by PTR-MS were conducted after mixing of terpenes, ozone and CCs, and time changes of volatile organic compounds (VOCs) concentrations were monitored. Results showed that, high-molecular weight intermediates disappeared gradually with elapsed time, though the production of high-molecular weight intermediates was observed at the beginning. This phenomenon suggested that the ozone oxidation of terpenes generated ultrafine particles. Coexistent CCs affected the ozone oxidation of α-pinene more than limonene

ヘテロ原子を含む芳香族化合物のT→S逆項間交差過程

金沢大学薬学部本研究の目的は、ヘテロ原子(O、N)を含む芳香族化合物の高い3重項(T_)から1重項(S_)へのT→S逆項間交差(RISC)をポンプ-プローブのレーザー2段励起分光で調べ、高い3重項(T_n)のダイナミックスを明らかにすることであった。従来のRISCの研究の対象は、メソ置換アントラセン類が多かったが、最近、3-ヒドロキシフラボン(3HF)および7-ヒロキシ-1-インダノン(7HIN)の光互変異性体のT^\u27_2→S^\u27_1RISCの研究が報告されていた。本研究では、カルボニル化合物である3HFの各種置換体の他芳香環窒素を有するジヒドロキシビピリジンについて、T→S RISCの機構を検討し、下記の成果を得た。1.3HFの各種置換体の光互変異性体の最低励起3重項(T\u27_1)励起に基ずくS\u27_1→S\u27_0蛍光を検出した。2.3HFの各種置換体の最低励起3重項(T_1)励起に基ずくS\u27_1→S\u27_0蛍光を検出した。これは、励起状態プロトン移動を示す分子のノルマル型3重項励起に因るS\u27_1生成の最初の報告となる。3.すなわち、3HFの各種置換体では、ノルマル型とその光互変異性体の最低励起3重項(T_1,T\u27_1)の何れを励起してもS\u27_1→S\u27_0蛍光が誘起される。これらの分離は、3重項増感および3重項消光の手法を用いた2段励起蛍光分光によりなされた。4.ジヒドロキシビピリジンの励起状態ダブルプロトン移動で生成する互変異性体のT\u27_1励起S\u27_1→S\u27_0蛍光を見いだした。これは、T\u27_1→S\u27_0 RISCを示す光互変異性体の第4の例である。その逆項間交差確率は、9,10-ジブロモアントラセンを標準物質とする相対決定法により、0.00063と見積られた。研究課題/領域番号:04640436, 研究期間(年度):1992出典：研究課題「ヘテロ原子を含む芳香族化合物のT→S逆項間交差過程」課題番号04640436（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） （https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-04640436/）を加工して作

芳香族N-オキシド化合物の光転位反応中間体の捕捉とその分光学的性質および反応性

金沢大学薬学部研究課題/領域番号:X00210----474230研究期間(年度):1979出典：「芳香族N-オキシド化合物の光転位反応中間体の捕捉とその分光学的性質および反応性」研究成果報告書　課題番号X00210----474230（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） （https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-X00210----474230/）を加工して作

GIPC-phospholipase D in plants

Previously, we detected an unknown sphingophospholipid in cabbage leaves and identified it as phytoceramide-1-phosphate (PC1P). We also found an enzyme activity that produces PC1P by glycosylinositol phosphoceramide (GIPC)-specific hydrolysis in cabbage leaves. To characterize the GIPC-specific phospholipase D (GIPC-PLD) activity, we investigated distributions of GIPC-PLD activity in 25 tissues of 10 plants. In most plants, the GIPC-PLD activity was the highest in roots. Young leaves of cabbage and Welsh onion had higher activities than corresponding aged outer leaves. The GIPC-PLD activities in leaves, stems and roots of mung bean were higher in the sprouting stage than in more mature stages. We also examined distribution of substrate GIPC and product PC1P, and found that GIPC was ubiquitously distributed at 50-280 nmol/g (wet wt) in tissues of plants, whereas PC1P was detectable (3-60 nmol/g wet wt.) only in tissues showing considerable GIPC-PLD activity. These results suggest a possibility that GIPC-PLD activity is involved in plant growth

Shock séptico, hipercalcemia y síndrome hemofagocítico por paracoccidioidomicosis en una niña de 3 años

Objetive: Report the case of a girl who presented septic shock, hypercalcemia and hemophagocytic syndrome due to paracoccidioidomycosis. Case report: 3-year-old female patient with 2-month illness characterized by fever, lymphadenopathy, weight loss, abdominal distention, and severe anemia. She arrived in poor general condition, developed septic shock and a hemophagocytic syndrome. The hypercalcemia and dermal lesions were striking. A cervical ganglion biopsy and bone marrow aspirate were performed. In the latter, images compatible with Paracoccidioides were found, which were then confirmed with Grocott's stain. She was treated with amphotericin B and trimethoprim-sulfamethoxazole. The evolution was favorable and serum calcium came back to normal ranges. Conclusion: Complications caused by paracoccidioidomycosis are rare; however, the epidemiological history and bone marrow aspirate should guide the diagnosis and allow prompt treatment.Objetivo: Reportar el caso de una niña que presentó shock séptico, hipercalcemia y síndrome hemofagocítico por paracoccidioidomicosis. Reporte de caso: Paciente mujer de 3 años con 2 meses de enfermedad caracterizada por fiebre, adenopatías, pérdida de peso, distensión abdominal y anemia severa. Llegó en mal estado general, desarrolló shock séptico y un síndrome hemofagocítico. Llamaba la atención la hipercalcemia y lesiones dérmicas. Se le realizó una biopsia de ganglio cervical y aspirado de médula ósea. En esta última se evidenciaron imágenes compatibles con Paracoccidioides, que fueron confirmadas con la tinción de Grocott del ganglio. Se trató con anfotericina B y trimetoprim-sulfametoxazol. La evolución fue favorable y el calcio sérico se mantuvo en rangos normales. Conclusión: Las complicaciones presentadas por paracoccidioidomicosis son raras; sin embargo, el antecedente epidemiológico y el aspirado de médula ósea pueden orientar el diagnóstico y permitir un tratamiento oportuno