Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.339
J. Yamamoto, Ryuji Hamada, T. Tsuboi
{"title":"Photochemical Reaction of Azoxybenzenes in the Presence of Acetic Acid.","authors":"J. Yamamoto, Ryuji Hamada, T. Tsuboi","doi":"10.1246/NIKKASHI.2002.339","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.339","url":null,"abstract":"","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86033205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Syntheses of Novel Net-worked Hybrid Copolymers with Alternative Tantalum-Organic Moieties.","authors":"Ryoichi Kudo, H. Matsui, M. Yoshihara","doi":"10.1246/NIKKASHI.2002.371","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.371","url":null,"abstract":"タンタルブトキシドと種々の有機ジオールとの反応を行ったところ，タンタル-有機基交互構造を有する新規ハイブリッド共重合体が生成した．また，生成物の形状は，導入する有機基の種類によって形状が変化することが判明した．さらに，生成物の電子物性を検討するためにESRスペクトルおよびab-initio分子軌道計算を行ったところ，共役系有機基を導入した系において，交互構造内で有機骨格よりタンタル原子上へ電子移動が生じていることが判明した．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87241619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.463
J. Yamamoto, K. Hamanaka, T. Tsuboi
When the starting materials 4-acetyl-ONN- and -NNO-azoxybenzene(1α and 1β, respectively) were heated in 70/80% sulfuric acid, α/β isomerization and the Wallach rearrangement to 4-acetyl-4′-hydroxyazobenzene (2) were observed. However, neither the o-hydroxyazobenzene nor 4-acetyl azobenzene was detected in the reaction product. The isomerization of 1α was faster than that of 1β, demonstrating the higher themodynamic stability of the latter.
{"title":"The Oxygen Transfer Reaction of 4-Acetylazoxybenzenes in Sulfuric Acid.","authors":"J. Yamamoto, K. Hamanaka, T. Tsuboi","doi":"10.1246/NIKKASHI.2002.463","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.463","url":null,"abstract":"When the starting materials 4-acetyl-ONN- and -NNO-azoxybenzene(1α and 1β, respectively) were heated in 70/80% sulfuric acid, α/β isomerization and the Wallach rearrangement to 4-acetyl-4′-hydroxyazobenzene (2) were observed. However, neither the o-hydroxyazobenzene nor 4-acetyl azobenzene was detected in the reaction product. The isomerization of 1α was faster than that of 1β, demonstrating the higher themodynamic stability of the latter.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87437290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.243
享 中山, 幹雄 樋口, 和義 上松
Four kinds of single crystals of hexagonal apatite type Ndx(SiO4)6O1.5x−12 (x = 8–9.33), which is an oxide ionic conductor, were prepared by the FZ method and samples for electrical measurements (the conductivity components parallel and perpendicular to the c-axis of single crystal) were prepared. The conductivities of the component parallel to the c-axis were higher about one order of magnitude, compared with those of the component perpendicular. The values of (Nd/Si) × 6 of four kinds of samples were 8.63, 8.67, 8.91 and 9.33 determined by electron probe micro-analysis. The conductivity was slightly increased with decreasing the value of (Nd/Si) × 6.
{"title":"アパタイト型Ndx(SiO4)6O1.5x−12単結晶のEPMAによって決定された組成と伝導率の関係","authors":"享 中山, 幹雄 樋口, 和義 上松","doi":"10.1246/NIKKASHI.2002.243","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.243","url":null,"abstract":"Four kinds of single crystals of hexagonal apatite type Ndx(SiO4)6O1.5x−12 (x = 8–9.33), which is an oxide ionic conductor, were prepared by the FZ method and samples for electrical measurements (the conductivity components parallel and perpendicular to the c-axis of single crystal) were prepared. The conductivities of the component parallel to the c-axis were higher about one order of magnitude, compared with those of the component perpendicular. The values of (Nd/Si) × 6 of four kinds of samples were 8.63, 8.67, 8.91 and 9.33 determined by electron probe micro-analysis. The conductivity was slightly increased with decreasing the value of (Nd/Si) × 6.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82554760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Physicochemical Properties of the Firmiana Platanifolia Mucilages.","authors":"Yukiko Fukagawa, H. Kouzai, Y. Kōzai","doi":"10.1246/NIKKASHI.2002.415","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.415","url":null,"abstract":"和紙抄造などに利用されているアオギリの粘質物を採取し，物理化学的特性や構成成分について研究を行った． アオギリの若葉や幹に被覆する酸性多糖類は，イオン交換水にて抽出した後メタノールで精製する．多糖類は，D-ガラクツロン酸，D-ガラクトース，L-アラビノースおよびL-ラムノースから構成されている．さらに粘質液を数日間放置すると粘度が低下する．アオギリ粘質物の酸による加水分解からアミノ酸であるL-グルタミン酸，L-アラニン，さらにはL-イソロイシン，L-バリン，L-リシン，L-チロシンおよびグリシンを得た．これらの結果は，アオギリに含まれる多糖類がきわめて複雑な構造を有し，その結果特有な物理的性質を与えていることと示唆している．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79974504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Distribution Characteristics of Fractionated Phosphorus in the Sediment Mud of the Tidal River.","authors":"H. Tatsumoto, T. Narita, M. Aikawa","doi":"10.1246/NIKKASHI.2002.427","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.427","url":null,"abstract":"感潮河川域における底質中の形態別リンの分布特性を把握するために花見川(千葉市)を選び，形態別リン濃度および他の項目との関連性について検討した． 底質の採取は9地点を選び，エクマンバージ採泥器を使用し，同時に流速も測定した． 形態別リンは，硫酸 · 硝酸分解抽出法により検出されるリンを全リン(T-P)とし，Williamsらの形態別分画定量法に基づいて得られたCDB-P，NaOH-PおよびHCl-Pの合計量を無機態リン(I-P)とした．有機態リン(Org-P)は，全リンと無機態リンとの差から求めた． 形態別リン濃度および流速の測定結果から，河川形状の変化により流速が遅くなる地点では，CDB-P，NaOH-PおよびHCl-Pが多く堆積し底質中の濃度が上昇することを認め，また上流地点より流速が速くなる地点では，底質中のCDB-PおよびNaOH-P濃度が減少することが明らかになり，現場実験においてもCDB-PおよびNaOH-P濃度と流速の関係を再確認した． 形態別リン濃度と同時に，底質のpH，底質中のFeおよびAl濃度も定量し，形態別リン濃度との関係を調べた． 上流地点よりpH値および底質中のAl濃度が高くなる地点では，CDB-P濃度が高い値を示した．また，CDB-P濃度とAl濃度との良好な相関性を得たことから，CDB-P堆積にはAlの加水分解過程におけるリンの吸着および沈降の寄与が大きいと推察された．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88178089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
二乙基醚(DEE)、二丙基醚(DPE)、二丁基醚(DBE)、二s-丁基醚(DSBE)、二辛基醚(DOE);用IR谱法研究二酰醚(DDE)和乙二醇二丁基醚[1,2-二丁基乙烷(DBOE)]中的溶解水形成的各簇物的状态，对热稳定性也进行了调查。这些簇与醚基上结合氢键的水分子([—O—·H2O])以及围绕它的簇([—O—·Cluster])，烷基直接相互作用产生的簇群(C1，C2)和围绕它们的大型集群(LC1, LC2, LC3)。烷基越长，醚基的氧原子的负性越大，结果，[- O -·Cluster]成为大的簇。烷基链越长，C1、C2的大小和量就越小，相反，LC1、LC2、LC3的大小就越大。C1在40—80°C时气化。另外，LC2、LC3随着升温而热破坏，形成了小集群。
{"title":"Structure and Thermal Behavior of Water Dissolved in Ethers Studied by FT-IR Spectroscopy.","authors":"K. Takaoka, Koichi Kobayashi, Masashi Takahashi, Y. Taru, Masahisa Takasago, M. Sone","doi":"10.1246/NIKKASHI.2002.313","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.313","url":null,"abstract":"ジエチルエーテル(DEE)，ジプロピルエーテル(DPE)，ジブチルエーテル(DBE)，ジ-s-ブチルエーテル(DSBE)，ジオクチルエーテル(DOE)，ジデシルエーテル(DDE)およびエチレングリコールジブチルエーテル[1,2-ジブトキシエタン(DBOE)]中の溶存水が形成する各クラスターの状態をIRスペクトル法で検討するとともに，熱安定性についても調べた． これらのクラスターは，エーテル基に水素結合した水分子([–O– · H2O])およびそれを取り巻くクラスター([–O– · Cluster])，アルキル基と直接相互作用して生じたクラスター群(C1，C2)とそれらを取り巻く大型のクラスター群(LC1，LC2，LC3)に分類された． アルキル基が長くなるほどエーテル基の酸素原子の陰性度が大きくなり，その結果，[–O– · Cluster]は大きいクラスターとなった．アルキル鎖が長くなるにつれ，C1，C2の大きさとその量は小さくなり，逆に，LC1，LC2，LC3のそれらは大きくなった． C1は，40–80 °Cで気化する．また，LC2，LC3は昇温とともに熱破壊して小クラスターとなった．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86876935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.261
Y. Fujiwara, Y. Ishikawa, Y. Amao
The properties of an optical sensor based on the oxygen-induced and temperature-induced luminescence quenching of tetrakis(pentafluorophenyl)porphyrinatoplatinum (PtTFPP) and 3,9-perylenedicarboxylic acid diisobutyl ester immobilized in a polystyrene film were investigated. The luminescence from PtTFPP in a polystyrene film was quenched by oxygen. On the other hand, the luminescence from 3,9-perylenedicarboxylic acid diisobutyl ester was not quenched by oxygen. Thus, the coincidence measurement for oxygen and temperature changes were attained using PtTFPP and 3,9-perylenedicarboxylic acid diisobutyl ester immobilized in polystyrene film.
{"title":"Properties of an Optical Sensor Based on Luminescence Quenching of Platinum Porphyrin and Perylene Immobilized in a Polystyrene Film.","authors":"Y. Fujiwara, Y. Ishikawa, Y. Amao","doi":"10.1246/NIKKASHI.2002.261","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.261","url":null,"abstract":"The properties of an optical sensor based on the oxygen-induced and temperature-induced luminescence quenching of tetrakis(pentafluorophenyl)porphyrinatoplatinum (PtTFPP) and 3,9-perylenedicarboxylic acid diisobutyl ester immobilized in a polystyrene film were investigated. The luminescence from PtTFPP in a polystyrene film was quenched by oxygen. On the other hand, the luminescence from 3,9-perylenedicarboxylic acid diisobutyl ester was not quenched by oxygen. Thus, the coincidence measurement for oxygen and temperature changes were attained using PtTFPP and 3,9-perylenedicarboxylic acid diisobutyl ester immobilized in polystyrene film.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91076700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalytic Performance in NO Reduction and Loading State of Precious Metal for Pt-Rh Loading Catalysts on Oxygen Storage Components.","authors":"H. Yamada, Seiji Miyoshi, K. Okamoto, H. Sumida, A. Takami","doi":"10.1246/NIKKASHI.2002.435","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.435","url":null,"abstract":"酸素貯蔵材(OSC)に貴金属を担持した触媒において，白金(Pt)とロジウム(Rh)の担持状態や触媒特性に及ぼす影響を，酸化セリウム(CeO2)，セリウム-ジルコニウム(Ce–Zr)複酸化物，セリウム-プラセオジム(Ce–Pr)複酸化物および酸化プラセオジム(Pr6O11)を用いて調べた．TPR結果から，Prを含んだOSCを担体にしたPt–Rh/Ce–Pr複酸化物とPt–Rh/Pr6O11の触媒は優れた酸素放出特性や水素(H2)の貯蔵特性を示した．これらの触媒は，他の二つの触媒と比べて，H2や一酸化炭素(CO)を還元剤にした一酸化窒素(NO)浄化反応に高い活性を発現することがわかった． XPS分析結果から，Pt–Rh/Ce–Pr複酸化物とPt–Rh/Pr6O11のPt表面はCeO2，Ce–Zr複酸化物に担持されたものと異なり，電子密度が希薄な状態である．EXAFS分析結果から，PtとRhは合金化しており，Pt–Rh/Ce–Pr複酸化物とPt–Rh/Pr6O11のRhはCeO2，Ce–Zr複酸化物に担持されたものに比べて金属に近い還元状態であることがわかった． 以上のことから，貴金属の担持状態や優れた触媒特性は，担体であるOSCとの強い相互作用に起因すると推察した．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88538443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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