{"title":"Intermolecular Charge-Transfer Interaction and Molecular Complex Formation of the Electrogenerated Organic Dianions.","authors":"N. Okumura, B. Uno","doi":"10.1246/NIKKASHI.2002.289","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.289","url":null,"abstract":"有機π電子系二価アニオンの特異的性質に基づく分子認識，それに伴うn-σおよびπ-π型電荷移動(CT)錯体生成能とその電気化学的制御に関する最近の研究成果を記した． 電解により生成するキノン類二価アニオン(PQ2−)の水素結合錯体の構造と電子状態を明らかにした．この水素結合は強いn-σ型電荷移動によって支えられ，キノンの構造的特徴を反映してπ電子系に多大な影響を与えた．水素結合はn-σ型電荷移動であるにもかかわらず，πフロンティア軌道によって引き起こされるPQ2−の機能を制御可能であることが示された．これらの結果は，生物活性キノンの機能に関する水素結合の役割に対して基礎的知見を与えるものと考えられる． 一方，TCNE2−およびクロラニル二価アニオン(CL2−)のは4nπ電子系のビフェニレンとπ-π型CT相互作用することを実験的に証明し，この錯体生成は二価アニオンが4nπ分子を分子軌道レベルで認識した多点の相互作用によることを明らかにした．この結果，電位制御によるHOMO-LUMO相互作用がスイッチされ，色と構造の異なる二つの安定な錯体生成系を提案することができた．この結果は，酸化還元反応に制御された分子化合物生成を用いる分子スイッチや機能性分子構築に基礎的な知見を与えるものと考えられる．","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":"78248649","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":"Polyaddition of Bifunctional Isoprene Prepolymer Terminated with Hydroxy Groups and Diisocyanates.","authors":"H. Kouzai, T. Mitsumata","doi":"10.1246/NIKKASHI.2002.409","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.409","url":null,"abstract":"ヒドロキシ基を両末端に結合したイソプレンプレポリマーがナトリウム-ナフタレンを開始剤としてイソプレンの溶液重合を行って，まずリビングプレポリマーとし，さらに乾燥酸素を通じて約75%の収率で得られた．このプレポリマーの分子量は1300–1500であり，1分子当たりのヒドロキシ基数は2.0–2.15であった．また，このプレポリマーのジイソシアナートによる重付加について若干検討した．反応溶媒としては，アニソール以外にN,N-ジメチルホルムアミドとジメチルスルホキシドが使用できる．得られたポリマーは黄色のスポンジゴム状で，一般の有機溶媒には不溶である．また，ガラス転移温度は73–78 °Cであった．","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":"91349704","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.2002.255
Yasuyuki Suzuki, Jun Li, Y. Maekawa, Masaru Yoshida, K. Maeyama, N. Yonezawa
The hydrophilic surface of poly(ethylene terephthalate) (PET) film, obtained by partial hydrolysis, was converted to hydrophobic one under dry air, saturated water vapor atmosphere, nitrogen, and vacuum at temperatures ranging from 0 to 80 °C. The hydrophilicity of the surface increased significantly faster under the saturated water vapor although it was the most hydrophilic in the examined conditions. From the dependence of the absolute temperature on the rate of hydrophilicity change for each storage condition, a discontinuous point at ca. 50 °C was observable only under the water vapor condition. This relation indicates that the appreciable acceleration of the hydrophilicity change on the surface under the hydrophilic condition might be resulted from the increase of the surface mobility due to the water adsorption on the PET surface.
{"title":"Conversion of Hydrophilic Surface of Poly(ethylene terephthalate) Film to Hydrophobic One under Hydrophilic Conditions.","authors":"Yasuyuki Suzuki, Jun Li, Y. Maekawa, Masaru Yoshida, K. Maeyama, N. Yonezawa","doi":"10.1246/NIKKASHI.2002.255","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.255","url":null,"abstract":"The hydrophilic surface of poly(ethylene terephthalate) (PET) film, obtained by partial hydrolysis, was converted to hydrophobic one under dry air, saturated water vapor atmosphere, nitrogen, and vacuum at temperatures ranging from 0 to 80 °C. The hydrophilicity of the surface increased significantly faster under the saturated water vapor although it was the most hydrophilic in the examined conditions. From the dependence of the absolute temperature on the rate of hydrophilicity change for each storage condition, a discontinuous point at ca. 50 °C was observable only under the water vapor condition. This relation indicates that the appreciable acceleration of the hydrophilicity change on the surface under the hydrophilic condition might be resulted from the increase of the surface mobility due to the water adsorption on the PET surface.","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":"83196887","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":"Production of Taxol and Related Taxoids by Callus Culture of Taxus cuspidata.","authors":"Jun-ichi Sakai, M. Ando, T. Uchiyama, Hajime Fujisawa, M. Kitabatake, Kazuki Toyoizumi, K. Hirose","doi":"10.1246/NIKKASHI.2002.231","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.231","url":null,"abstract":"再生可能資源として入手の容易な日本イチイ(Taxus cuspidata)を新規抗癌剤Taxol®(Paclitaxel)(1)ならびに1の関連タキソイドの供給源として検討するため，日本イチイから誘導したカルス(イチイ培養細胞)に着目し，カルスの誘導方法，安定した増殖培養条件，1ならびにその関連タキソイド類の分離，生産方法を検討した． その結果，イチイカルスの誘導および安定した増殖を示す培養条件を見いだし，その生産物の抽出，分離方法を詳細に検討することにより，Taxol(1)を含め1の生合成における中間段階と考えられるタキソイド合計10種類とアビエタン1種類を単離同定した．また，本カルスはイチイ樹皮の含有量に匹敵する1の生産(乾燥カルス基準で0.01%)と，低酸化度のタキソイドTaxuyunnanine C(2)を始めとするその14位同族アシル化体3–6を極めて高い収率(乾燥カルス基準で総計0.49%)で生産しており，この結果は1の本カルスによる生産の可能性ならびに1および1の修飾化合物へのタキサン骨格供給源としての可能性を示唆する．","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":"88527145","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":"Flow Characteristics and Saline Wedge of the Density Flow in a Tidal River.","authors":"H. Tatsumoto, J. Park, M. Aikawa","doi":"10.1246/NIKKASHI.2002.77","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.77","url":null,"abstract":"塩水くさびが存在する流れの流動特性をは握するために長方形断面の開水路を用いて塩水くさびの発生と流動の実験を行った．塩水くさびは全体的に安定して目視観測を容易にしたため，その界面層の観測は可視化手法で行った．実験の結果，塩水くさびは十分に再現され，塩水くさびの先端は相対密度と上流部の流量によってその形状が変化することが認められた．下流部の淡水深の厚さはリチャドーソン数に依存性を持っていることがわかった．また，はく離点付近の希釈の度合は密度層内のFioとの関数で表示できた．","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":"90539544","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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