{"_buckets": {"deposit": "bc7d89b3-a40a-4717-b980-86bae293189d"}, "_deposit": {"id": "2565", "owners": [], "pid": {"revision_id": 0, "type": "depid", "value": "2565"}, "status": "published"}, "_oai": {"id": "oai:niigata-u.repo.nii.ac.jp:00002565", "sets": ["454", "425"]}, "item_5_alternative_title_1": {"attribute_name": "その他のタイトル", "attribute_value_mlt": [{"subitem_alternative_title": "Kinetic Analysis of Reactivity of Substituted Benzoic Acids in the T-for-H Exchange Reaction"}]}, "item_5_biblio_info_6": {"attribute_name": "書誌情報", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2008", "bibliographicIssueDateType": "Issued"}, "bibliographicIssueNumber": "4", "bibliographicPageEnd": "240", "bibliographicPageStart": "233", "bibliographicVolumeNumber": "57", "bibliographic_titles": [{"bibliographic_title": "Radioisotopes"}, {"bibliographic_title": "Radioisotopes", "bibliographic_titleLang": "en"}]}]}, "item_5_description_4": {"attribute_name": "抄録", "attribute_value_mlt": [{"subitem_description": "トリチウム(^3H又はT)が環境中の種々の物質の官能基に及ぼす影響を定量評価するために,T標識ポリ(ビニルアルコール)と各種脂環式アルコール(又はカルボン酸)との間の水素同位体交換反応(T-for-H交換反応)を,50～90℃の温度範囲で固液反応の形で観測した。得られた観測データにA\"-McKayプロット法を適用することで,この反応の速度定数(k)を得た。このkを用いることで,各試料物質の環中の炭素数とその物質の反応性との関係を定量比較することができた。更に,各試料物質のOH基(又はCOOH基)のH原子に直結するO原子上の相対電荷が反応性に及ぼす影響を明らかにするため,MOPAC法を用いた。以上の結果と以前得られた結果とから,T-for-H交換反応における脂環式アルコール(及びカルボン酸)に関して,次のことがわかった。(1)脂環式アルコール(及びカルボン酸)の反応性は,温度に依存する。(2)その物質中の官能基が直結している母体の炭素数が増加するにつれ,反応性は低下する。(3)脂環式カルボン酸の反応性は脂環式アルコールよりも低く,脂環式アミンより高い傾向にある。(4)MOPAC法により求められたO原子の相対電荷とkとの間には,アルコールについては相関性があるが,カルボン酸については顕著な関係は認められない。(5)側鎖を持つ脂環式カルボン酸は,これを持たないものよりも反応性が低い。(6)脂環式カルボン酸は脂肪族直鎖状カルボン酸よりも反応性が高いと推測される。(7)目的物質の溶媒として1,4-ジオキサンを用いるとp-キシレンを用いたときよりも反応性が低くなる傾向がある。(8)MOPAC法とA\"-McKayプロット法とを用いると,各種脂環式化合物の実態的分析が一層可能となる。(9)本研究で行った種々の手法は,環境に及ぼすTの影響評価を行うための手法として有用である。", "subitem_description_type": "Abstract"}, {"subitem_description": "In order to quantitatively evaluate the influence of tritium (^3H or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly-(vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90℃. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying the A\"-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring. the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of aliphatic normal carboxylic acid. (7) The reactivity of these materials dissolved in 1,4-dioxane is smaller than that in p-xylene. (8) Using both the MOPAC and the A\"-McKay plot methods, the actual analysis of aliphatic cyclic alcohols can be more possible. (9) The method used in this work is useful for evaluating influence of T on environment.", "subitem_description_type": "Abstract"}]}, "item_5_full_name_3": {"attribute_name": "著者別名", "attribute_value_mlt": [{"nameIdentifiers": [{"nameIdentifier": "37806", "nameIdentifierScheme": "WEKO"}], "names": [{"name": "Sawada, Yoshinori"}]}, {"nameIdentifiers": [{"nameIdentifier": "37807", "nameIdentifierScheme": "WEKO"}], "names": [{"name": "Imaizumi, Hiroshi"}]}, {"nameIdentifiers": [{"nameIdentifier": "37808", "nameIdentifierScheme": "WEKO"}], "names": [{"name": "Kano, Naoki"}]}]}, "item_5_publisher_7": {"attribute_name": "出版者", "attribute_value_mlt": [{"subitem_publisher": "日本アイソトープ協会"}]}, "item_5_relation_37": {"attribute_name": "部分である", "attribute_value_mlt": [{"subitem_relation_type": "isPartOf", "subitem_relation_type_id": {"subitem_relation_type_id_text": "http://hdl.handle.net/10191/7010", "subitem_relation_type_select": "URI"}}]}, "item_5_select_19": {"attribute_name": "著者版フラグ", "attribute_value_mlt": [{"subitem_select_item": "publisher"}]}, "item_5_source_id_11": {"attribute_name": "書誌レコードID", "attribute_value_mlt": [{"subitem_source_identifier": "AN00351589", "subitem_source_identifier_type": "NCID"}]}, "item_5_source_id_9": {"attribute_name": "ISSN", "attribute_value_mlt": [{"subitem_source_identifier": "00338303", "subitem_source_identifier_type": "ISSN"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "澤田, 佳則"}], "nameIdentifiers": [{"nameIdentifier": "37803", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "今泉, 洋"}], "nameIdentifiers": [{"nameIdentifier": "37804", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "狩野, 直樹"}], "nameIdentifiers": [{"nameIdentifier": "37805", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2019-07-29"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "2009030062.pdf", "filesize": [{"value": "555.7 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 555700.0, "url": {"label": "2009030062.pdf", "url": "https://niigata-u.repo.nii.ac.jp/record/2565/files/2009030062.pdf"}, "version_id": "0639be6c-e889-4db8-9d28-2bf86cf1d85b"}]}, "item_keyword": {"attribute_name": "キーワード", "attribute_value_mlt": [{"subitem_subject": "tritium", "subitem_subject_scheme": "Other"}, {"subitem_subject": "substituted hydroxybenzoic acid", "subitem_subject_scheme": "Other"}, {"subitem_subject": "T-for-H exchange reaction", "subitem_subject_scheme": "Other"}, {"subitem_subject": "A\"-Mckay plot method", "subitem_subject_scheme": "Other"}, {"subitem_subject": "Hammett rule", "subitem_subject_scheme": "Other"}, {"subitem_subject": "liquid-solid reaction", "subitem_subject_scheme": "Other"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "jpn"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "journal article", "resourceuri": "http://purl.org/coar/resource_type/c_6501"}]}, "item_title": "T-for-H交換反応における安息香酸誘導体の速度論的反応解析", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "T-for-H交換反応における安息香酸誘導体の速度論的反応解析"}, {"subitem_title": "T-for-H交換反応における安息香酸誘導体の速度論的反応解析", "subitem_title_language": "en"}]}, "item_type_id": "5", "owner": "1", "path": ["454", "425"], "permalink_uri": "http://hdl.handle.net/10191/7166", "pubdate": {"attribute_name": "公開日", "attribute_value": "2009-04-06"}, "publish_date": "2009-04-06", "publish_status": "0", "recid": "2565", "relation": {}, "relation_version_is_last": true, "title": ["T-for-H交換反応における安息香酸誘導体の速度論的反応解析"], "weko_shared_id": null}