1994 Fiscal Year Annual Research Report

溶液反応における動的過程の研究と分析化学への応用

Research Project

Project/Area Number	06303005
Research Institution	University of Tsukuba
Principal Investigator	河嶌拓治筑波大学, 化学系, 教授 (50041760)
Co-Investigator(Kenkyū-buntansha)	田端正明佐賀大学, 理工学部, 教授 (40039285) 本水昌二岡山大学, 理学部, 教授 (50032826) 船橋重信名古屋大学, 理学部, 教授 (30022700) 大橋弘三郎茨城大学, 理学部, 教授 (60007763) 渡辺寛人北海道大学, 工学部, 教授 (80002856)
Keywords	溶液反応 / 動的過程 / 化学発光 / 接触作用 / 溶媒抽出 / フローインジェクション分析法 / イオン会合反応 / 溶存錯体の構造
Research Abstract	ルミノール化学発光(CL)における遅延現象に関し,ルミノールラジカルの生成を認め,これがCLを発現することを明らかにした.ルミノール化学発光を利用する鉄(II,III)中の微量鉄(II)の超微量分析も行われた.逆ミセルをCLのミクロ反応場として用いる分析法においてCL反応に対する金属錯体の影響及びそれらの反応性との関係について系統的な研究が行われた. 金属ポリフィリンの生成反応における反応活性中間体の生成をラピッドスキャン分光光度法により推定し,EXAFS法によりその存在と構造を明らかにし,更に拡張ポルフィリンとフィ化物イオンとの反応についての検討が行われた.そのほかペルオキソクロム中間体の構造解析が時間分解EXAFSにより行われ新しい知見が得られた.ラジカルが関与する誘発電子移動反応の速度論的解析が行われ,微量分析への展開が期待された金属錯体の生成反応機構の考察から速度差分析への応用が期待され,金属イオンの接触作用を利用する接触分析法及び接触滴定法の研究が行われた.接触滴定法においては10^<-6>オーダーの鉄(III)の定量が可能となった. トリフェニルメタン系染料陽イオンに関する平衡論的・速度論的研究が行われ,それらの研究結果に基づいて分析化学に有用な陽イオン染料の合成開発が行われた.溶媒抽出に関し,バナジウムのジチオカルバミン酸塩による抽出の速度論的検証により,塩化物イオン及び臭化物イオンなどの補助錯化剤が共在すると高選択的に分離できることが明らかにされた.銅(II),コバルト(III),鉄(II),ニッケル(II)などのキノリルアゾ化合物の逆相クロマトグラフィーにおける分離挙動が詳細に検討され,新しい知見が得られた.生命と無機リン酸化合物の関わりから,ATPの酵素による加水分解反応について,FIA,HPLC,^<31>PNMRを利用して速度論的な研究が行われ興味ある結果が得られた.

Research Products
(24 results)

All Other

All Publications (24 results)

[Publications] T.Kamidate, M.Katoh, T.Segawa, H.Watanabe: "Peroxyoxalate chemiluminescent assay of ascorbic acid based on autoxidation with oxygen in reversed micelle" Chem.Lett.113-116 (1994)
[Publications] T.Saitoh, H.Tani, T.Kamidate, T.Kamataki, H.Watanabe: "Polymerinduced phase separation in aqueous micellar solutions of alkylglucoside for protein extraction" Anal.Sci. 10. 299-303 (1994)
[Publications] T.Saitoh, M.Okayama, T.Kamidate, H.Watanabe, K.Haraguchi: "Solvent extraction of lanthanoids (III) and yttrium (III) with N-(2,2-dimethylpentanoyl)-N-phenylhydroxylamine," Bull.Chem.Soc.Jpn.67. 1002-1006 (1994)
[Publications] T.Segawa, S.Suehara, T.Kamidate, H.Watanabe: "Oscillatory chemiluminescence during peroxidation of umbelliferone catalyzed by horseradish peroxidase" Bill.Chem.Soc.Jan.67. 1301-1305 (1994)
[Publications] T.Kamidate, A.Ishikawa, T.Segawa, H.Watanabe: "Time-Resolved luminol chemiluminescence for simultaneous determination of cobalt(II) and copper(II)" Chem.Lett.1123-1126 (1994)
[Publications] T.Saitoh, M.Ohaba, T.Kamidate, H.Watanabe: "Distribution of pyridylazophenols and their metal chelates between two phases separated from micellar solution of octy-β-D-thioglucoside in the presence of polyethylene glycol" Anal.Sci.10. 379-382 (1994)
[Publications] 中井泉,守口正生,鈴木拓,河嶌拓治,下条信弘: "全反射蛍光X線分析法による急性ヒ素中毒マウス組織中の微量ヒ素の定量," X線分析の進歩. 25. 269-280 (1994)
[Publications] 手嶋紀雄,中野恵文,河嶌拓治: "フローインジェクション分析法による微量元素の接触分析法" J.Flow Injec.Anal.11. 7-23 (1994)
[Publications] M.Kurihara, K.Ozutsumi, T.Kawashima: "Thermodynamics of complexation of manganese (II) and zinc (II) ions with pyridine,3-methyl- and 4-methyl-pyridine cyanomethane" J.Chem.Soc.,Dalton Trans.3267-3271 (1994)
[Publications] M.Kurihara, K.Ozutsumi, T.Kawashima: "An X-ray diffraction study on the structure of 4-methylpyridine in N,N-dimethylformamide" Inorg.Chim.Acta. 228. 255-260 (1995)
[Publications] T.Yasui, A.Yuchi, H.Yamada, H.Wada: "Reversed-phase high-performance liquid chromatographic behaviour of some metal 1-(2-pyridylazo)-2-naphthol chelates" J.Chromatogr. 659. 359-365 (1994)
[Publications] T.Ishizuki, K.Matsumoto, A.Yuchi, T.Ozawa, H,Yamada, H.Wada: "Flow-injection spectrophotometric determination of cadmium with quinolvlazo compound after on-line separation using a silica gel column" Talanta. 41. 799-805 (1994)
[Publications] T.Segawa, H.Ishikawa, T.Kamidate, H.Watanabe: "Micelle-Enhanced fluorescein chemiluminescence catatlyzed by horseradish peroxidase for the determination of hydrogen peroxide" Anal.Sci.10. 589-593 (1994)
[Publications] T.Kamidate, A.Katayama, H.Ichihashi,H.Watanabe: "Characterization of peroxidases in luminol chemiluminescence coupled with copper-catalysed oxidation of cysteamine" J.Biolumin.Chemilumin.9. 279-286 (1994)
[Publications] T.Saito, M.Okuyama, M.Minagawa, T.Kamidate, H.Watanabe, K.Haraguchi: "Solvent extraction of lanthanoids (III) and yttrium (III) with N-alkylcarbonyl-N-(4-chlorophenyl) hydroxylamines" Bill.Chem.Soc.Jan.67. 2107-2110 (1994)
[Publications] T.Kamidate, N.Kida, T.Kamataki,H.Watanabe: "Luminol chemiluminescent assay of cytochrome b_s" Anal.Biochem.223. 325-327 (1994)
[Publications] T.Kamidate, N.Kida, H.Ichihashi,H.Watanabe: "Role amino thiols as radical quenchers in delayed chemiluminescence of luminol catalyzed by horseradish peroxidase" Anal.Sci. 11. 169-173 (1995)
[Publications] E.Purnamawaty, T.Amimoto, H.Imura, Y.Usui, K.Ohashi: "Extraction equilibium of molybdenum (VI) with severl alkylated 8-quinolinol derivatives" Anal.Sci.749-753 (1994)
[Publications] T.Hamaya, K.Hiratani, K.Ohashi: "Preparation of water soluble polymer with 8-quinolinol group and its specific reactivity with Cd(II)" Chem.Lett. 615-618 (1994)
[Publications] T.Hamaya, K.Hiratani, K.Ohashi: "Ultraviolet spectrophotometric studies of the reactivity of a water-soluble polymer containing pendant 8-hydroxyquinoline moieties with metal ions" Macromol.Chem.Phys.195. 2739-2746 (1994)
[Publications] Y.Feng, H.Imura, K.Ohashi: "Extraction behavior of DI-m-oxo-bis(oxomolybdenum(V)] with 2-methyl-5-octyloxymethyl-8-quinolinol" Bull.Chem.Soc.Jan.(in press).
[Publications] C.X.Ren, F.Ynqi, H.Imura, K.Hiratani, K.Ohashi: "The selective preconcentration and separation of a trace amount of copper(II) with poly [N-(8-hydroxy-5-quinolylmethyl)-4-aminomethylstyrene] resin" Anal.Sci.(in press.).
[Publications] N.Teshima, H.Itabashi, T.Kawashima: "Effect of ligands on the iron(III)/iron(II) system and its novel application to simultaneous flow injection determination of vanadium(IV) and vanadium(V)" Anal.Sci. 10. 207-212 (1994)
[Publications] S.Nakano, M.Sakai, M.Kurachi, T.Kawashima: "Kinetic determination of iron based on its catalytic action on the oxidative coupling of 4-aminoantipyrine with N,N-dimethylaniline," Microchem.J.49. 298-304 (1994)

1994 Fiscal Year Annual Research Report

溶液反応における動的過程の研究と分析化学への応用

Principal Investigator

河嶌 拓治 筑波大学, 化学系, 教授 (50041760)

Research Products

[Publications] T.Kamidate, M.Katoh, T.Segawa, H.Watanabe: "Peroxyoxalate chemiluminescent assay of ascorbic acid based on autoxidation with oxygen in reversed micelle" Chem.Lett.113-116 (1994)

[Publications] T.Saitoh, H.Tani, T.Kamidate, T.Kamataki, H.Watanabe: "Polymerinduced phase separation in aqueous micellar solutions of alkylglucoside for protein extraction" Anal.Sci. 10. 299-303 (1994)

[Publications] T.Saitoh, M.Okayama, T.Kamidate, H.Watanabe, K.Haraguchi: "Solvent extraction of lanthanoids (III) and yttrium (III) with N-(2,2-dimethylpentanoyl)-N-phenylhydroxylamine," Bull.Chem.Soc.Jpn.67. 1002-1006 (1994)

[Publications] T.Segawa, S.Suehara, T.Kamidate, H.Watanabe: "Oscillatory chemiluminescence during peroxidation of umbelliferone catalyzed by horseradish peroxidase" Bill.Chem.Soc.Jan.67. 1301-1305 (1994)

[Publications] T.Kamidate, A.Ishikawa, T.Segawa, H.Watanabe: "Time-Resolved luminol chemiluminescence for simultaneous determination of cobalt(II) and copper(II)" Chem.Lett.1123-1126 (1994)

[Publications] T.Saitoh, M.Ohaba, T.Kamidate, H.Watanabe: "Distribution of pyridylazophenols and their metal chelates between two phases separated from micellar solution of octy-β-D-thioglucoside in the presence of polyethylene glycol" Anal.Sci.10. 379-382 (1994)

[Publications] 中井 泉,守口正生,鈴木 拓,河嶌拓治,下条信弘: "全反射蛍光X線分析法による急性ヒ素中毒マウス組織中の微量ヒ素の定量," X線分析の進歩. 25. 269-280 (1994)

[Publications] 手嶋紀雄,中野恵文,河嶌拓治: "フローインジェクション分析法による微量元素の接触分析法" J.Flow Injec.Anal.11. 7-23 (1994)

[Publications] M.Kurihara, K.Ozutsumi, T.Kawashima: "Thermodynamics of complexation of manganese (II) and zinc (II) ions with pyridine,3-methyl- and 4-methyl-pyridine cyanomethane" J.Chem.Soc.,Dalton Trans.3267-3271 (1994)

[Publications] M.Kurihara, K.Ozutsumi, T.Kawashima: "An X-ray diffraction study on the structure of 4-methylpyridine in N,N-dimethylformamide" Inorg.Chim.Acta. 228. 255-260 (1995)

[Publications] T.Yasui, A.Yuchi, H.Yamada, H.Wada: "Reversed-phase high-performance liquid chromatographic behaviour of some metal 1-(2-pyridylazo)-2-naphthol chelates" J.Chromatogr. 659. 359-365 (1994)

[Publications] T.Ishizuki, K.Matsumoto, A.Yuchi, T.Ozawa, H,Yamada, H.Wada: "Flow-injection spectrophotometric determination of cadmium with quinolvlazo compound after on-line separation using a silica gel column" Talanta. 41. 799-805 (1994)

[Publications] T.Segawa, H.Ishikawa, T.Kamidate, H.Watanabe: "Micelle-Enhanced fluorescein chemiluminescence catatlyzed by horseradish peroxidase for the determination of hydrogen peroxide" Anal.Sci.10. 589-593 (1994)

[Publications] T.Kamidate, A.Katayama, H.Ichihashi,H.Watanabe: "Characterization of peroxidases in luminol chemiluminescence coupled with copper-catalysed oxidation of cysteamine" J.Biolumin.Chemilumin.9. 279-286 (1994)

[Publications] T.Saito, M.Okuyama, M.Minagawa, T.Kamidate, H.Watanabe, K.Haraguchi: "Solvent extraction of lanthanoids (III) and yttrium (III) with N-alkylcarbonyl-N-(4-chlorophenyl) hydroxylamines" Bill.Chem.Soc.Jan.67. 2107-2110 (1994)

[Publications] T.Kamidate, N.Kida, T.Kamataki,H.Watanabe: "Luminol chemiluminescent assay of cytochrome b_s" Anal.Biochem.223. 325-327 (1994)

[Publications] T.Kamidate, N.Kida, H.Ichihashi,H.Watanabe: "Role amino thiols as radical quenchers in delayed chemiluminescence of luminol catalyzed by horseradish peroxidase" Anal.Sci. 11. 169-173 (1995)

[Publications] E.Purnamawaty, T.Amimoto, H.Imura, Y.Usui, K.Ohashi: "Extraction equilibium of molybdenum (VI) with severl alkylated 8-quinolinol derivatives" Anal.Sci.749-753 (1994)

[Publications] T.Hamaya, K.Hiratani, K.Ohashi: "Preparation of water soluble polymer with 8-quinolinol group and its specific reactivity with Cd(II)" Chem.Lett. 615-618 (1994)

[Publications] T.Hamaya, K.Hiratani, K.Ohashi: "Ultraviolet spectrophotometric studies of the reactivity of a water-soluble polymer containing pendant 8-hydroxyquinoline moieties with metal ions" Macromol.Chem.Phys.195. 2739-2746 (1994)

[Publications] Y.Feng, H.Imura, K.Ohashi: "Extraction behavior of DI-m-oxo-bis(oxomolybdenum(V)] with 2-methyl-5-octyloxymethyl-8-quinolinol" Bull.Chem.Soc.Jan.(in press).

[Publications] C.X.Ren, F.Ynqi, H.Imura, K.Hiratani, K.Ohashi: "The selective preconcentration and separation of a trace amount of copper(II) with poly [N-(8-hydroxy-5-quinolylmethyl)-4-aminomethylstyrene] resin" Anal.Sci.(in press.).

[Publications] N.Teshima, H.Itabashi, T.Kawashima: "Effect of ligands on the iron(III)/iron(II) system and its novel application to simultaneous flow injection determination of vanadium(IV) and vanadium(V)" Anal.Sci. 10. 207-212 (1994)

[Publications] S.Nakano, M.Sakai, M.Kurachi, T.Kawashima: "Kinetic determination of iron based on its catalytic action on the oxidative coupling of 4-aminoantipyrine with N,N-dimethylaniline," Microchem.J.49. 298-304 (1994)

河嶌拓治筑波大学, 化学系, 教授 (50041760)

[Publications] 中井泉,守口正生,鈴木拓,河嶌拓治,下条信弘: "全反射蛍光X線分析法による急性ヒ素中毒マウス組織中の微量ヒ素の定量," X線分析の進歩. 25. 269-280 (1994)