1995 Fiscal Year Annual Research Report

高効率発光を指向した化学発光・生物発光の基礎的研究

Research Project

Project/Area Number	06303003
Research Institution	Ochanomizu University
Principal Investigator	前田侯子お茶の水女子大学, 理学部, 教授 (40017190)
Co-Investigator(Kenkyū-buntansha)	今井一洋東京大学, 薬学部, 教授 (50012620) 松本正勝神奈川大学, 理学部, 教授 (10260986) 木村勝岡山大学, 理学部, 助教授 (30033442) 磯部稔名古屋大学, 農学部, 教授 (00023466) 大橋守電気通信大学, 電気通信学部, 教授 (70015535)
Keywords	化学発光 / 生物発光 / 発光効率 / セレンテラジン / ジオキセタン / ルシフェリン / 発光機構 / 電子移動発光
Research Abstract	化学発光は化学反応のエネルギーによって、励起状態の分子あるいは原子が生成し、それが基底状態に戻る時に過剰のエネルギーを光として放出する現象である。生物発光もそれぞれの発光生物に特有の発光基質である例えば蛍ルシフェリン、ウミホタルルシフェリン等の化学発光といえよう。化学発光の多くは酸化反応によりジオキセタンあるいはジオキセタノンなどの不安定な中間体を経由し、その熱分解によって励起状態のカルボニル化合物が生成する場合が殆どであるが、励起状態生成の機構についてはなお不明の点が多い。以上のことをふまえて本研究では12名の研究者が様々な視点から、また様々なアプローチの方法によって、生命の神秘とも深く係わっていると思われる発光現象に迫り、以下に記すような成果を得た。ウミホタルルシフェリンやオワンクラゲ等の海産生物の発光体成分であるイミダゾピラジノンから得られるジオキセタノンの構造を初めて明らかにした。ロフィンの化学発光では導入する置換基の組合せにより、励起状態への変換効率が0.8と大きい場合を見出し、電子移動の関与を示唆した。これ迄微弱発光として肉眼で見えなかったフェノチアジン誘導体の化学発光機構を明かにし、発光も眼に見える強度で発光スペクトルを測定できる条件を見出した。また電子豊富な二重結合を持つ化合物と分子状酸素との発光機構を明らかにした。様々なアリールジオキセタンの合成に成功し、その熱分解反応を試みてジオキセタンの構造と発光強度、発光時間、発光波長との関連を明らかにすることができた。ジオキセタンの熱分解反応を量子化学的に検討した結果では、ジオキセタン環を構成する炭素上に電子供与基が存在する方が発光が強くなること、また電荷移動が関与することが見出されている。その他にも多くの成果が得られている。

Research Products
(28 results)

All Other

All Publications (28 results)

[Publications] K.Maeda: "Mechanism of the chemiluminescence of biisoquinolinium salts" J.Chem.Soc.,Perkin Trans.2. 121-126 (1996)
[Publications] T.Hirano: "Chemi-and Bio-luminescence Properties of Coelenterazine Analogues Possessing an Adamantyl Group" J.Chem.Soc.,Chem.Commun.1135-1136 (1995)
[Publications] F.Q.Chen: "A potential photoaffinity probe for labelling the active site of aequorin:a photolabile coelenterazire analogue with a trifluoromethyldiazirine group" J.Chem.Soc.,Perkin Trans.1. 2129-2134 (1995)
[Publications] T.Matsuno: "Mass Spectrometric Investigation of Structures of Intermediates in Acridine Chemiluminescence" J.Mass Spectrom.Soc.,Jpn.(in press). (1996)
[Publications] M.Isobe: "New Analysis Method for Protein Phosphatase Type 2A Inhibitors Using the Firefly Bioluminescence System" Biosci.Biotech.Biochem.59. 2235-2238 (1995)
[Publications] M.Ohto: "Involvement of Ca^<2+>-signaling in the sugar-inducible expression of genes coding for sporamin and β-amylase of sweet potato" The Plant Journal. 7. 297-307 (1995)
[Publications] K.Teranishi: "Efficient preparation of alkoxymethyl carbonates by using potassium carbonate,chloromethyl alkyl ethers and alcohols" Bull.Chem.Soc.Jpn.68. 309-314 (1995)
[Publications] K.Teranishi: "One-step synthesis of novel carbonate,alkoxymethyl carbonate,from alcohol and chloromethyl alkyl ether using silver carbonate" Synthesis. 176-180 (1995)
[Publications] K.Satake: "Rearrangement of Bicyclo[2.2.2]octa-2,5-diene and Bicyclo-[3.2.2]nona-6,8-diene under the Conditions of Bromination" Bull.Chem.Soc.Jpn.69(in press). (1996)
[Publications] H.Okamoto: "Characterization of a Longicyclic[2,2,2,2]conjugated π System in 1,4-Difluorobenzene-Naphthalene Biplanemer" Bull.Chem.Soc.Jpn.68. 3557-3562 (1995)
[Publications] M.Matsumoto: "Effect of allylic oxygen on the reaction pathways of singlet oxygenation:selective formation of 1,2-dioxetanes from 1-alkoxymethyl-2-aryl-1-tert-butyl-2-methoxyethylenes" Tetrahedron Lett.37(in press). (1996)
[Publications] M.Matsumoto: "Synthesis and chemiluminescence of 3-biphenylyl-4,4-diisopropyl-3-methoxy-1,2-dioxetanes" Heterocycles. 41. 2419 (1995)
[Publications] K.Usami: "Two Luminescent Intermediates of Coelenterazine Analog,peroxide and Dioxetanone,Prepared by Direct Photooxygenation at Low Temperature" Tetrahedron Lett.36. 8613-8616 (1995)
[Publications] K.Usami: "Chemiluminescent Characters of Hydroperoxide and Dioxetanone of Coelenterate Luciferin Analog Prepared by Low-Temperature Photooxygenation" Chem.Lett.(in press). (1996)
[Publications] M.-C.Rho: "Zooxanthellatoxin-A,a novel polyoxygenated long chain compound,activates rabbit platelets,mediated via Ca^<2+> influx followed by the release of thromboxane A2 in an external Ca^<2+>-dependent manner" Br.J.Pharmacol.1996 ((in press))
[Publications] H.Nakamura: "Synthesis of 5-and 3,5-Substituted 2-Amino-pyrazines by Pd Mediated Still Coupling" Synlett. 1277-1278 (1995)
[Publications] H.Nakamura: "Zooxanthellatoxin-A,a Potent Vasoconstrictive 62-membered Lactone from a Symbiotic Dinoflagellate" J.Am.Chem.Soc.117. 550-551 (1995)
[Publications] K.Teranishi: "Synthesis of a model for the functional part of photoprotein aequorin" Biosci.Biotech.Biochem.59. 104-107 (1995)
[Publications] M.Matsumoto: "Thermal stability and chemiluminescence of 3-alkoxy-3-aryl-4,4-diisopropyl-1,2-dioxetanes" J.Chem.Soc.,Chem.Commun.431-432 (1995)
[Publications] M.Kitamura: "A new highly sensitive chemiluminescent assay of alkaline phosphatase using lucigenin and its application to enzyme immunoassay" J.Biolumin.Chemilumin.10. 1-7 (1995)
[Publications] H.Sasamoto: "Chemiluminescent enzymatic assay for cholesterol in serum using lucigenin" Anal.Chim.Acta. 310. 347-353 (1995)
[Publications] H.Sasamoto: "Highly sensitive immunological assays for human chorionic gonadotropin and prostatic acid phosphate using phenacyl phosphate as chemiluminescent label" Anal.Chim.Acta. 309. 221-225 (1995)
[Publications] H.Sasamoto: "Chemiluminescent assay of alkaline phosphatase using phenacvl phosphate" Anal.Chim.Acta. 306. 161-165 (1995)
[Publications] A.Tsuji: "Recent advances of chemiluminescent and bioluminescent assay" Jpn.J.Electroph.39. 301-309 (1995)
[Publications] P.Prados: "Generation of an active intermediate during the storage of a peroxyoxalate chemi-luminescence reagent solution under the presence of strong carboxylic acids" Anal.Sci.11. 575-580 (1995)
[Publications] 中村英士: "有機化学からみた渦鞭毛藻" 藻類. 43. 23-30 (1995)
[Publications] 前田昌子: "化学発光エンザイムイムノアッセイの原理と実際" 日本臨床. 53. 2096-2099 (1995)
[Publications] A.Tsuji: "Nonisotopic Probing,Blotting and Sequencing" Academic Press Inc., 10 (1995)

1995 Fiscal Year Annual Research Report

高効率発光を指向した化学発光・生物発光の基礎的研究

Principal Investigator

前田 侯子 お茶の水女子大学, 理学部, 教授 (40017190)

Research Products

[Publications] K.Maeda: "Mechanism of the chemiluminescence of biisoquinolinium salts" J.Chem.Soc.,Perkin Trans.2. 121-126 (1996)

[Publications] T.Hirano: "Chemi-and Bio-luminescence Properties of Coelenterazine Analogues Possessing an Adamantyl Group" J.Chem.Soc.,Chem.Commun.1135-1136 (1995)

[Publications] F.Q.Chen: "A potential photoaffinity probe for labelling the active site of aequorin:a photolabile coelenterazire analogue with a trifluoromethyldiazirine group" J.Chem.Soc.,Perkin Trans.1. 2129-2134 (1995)

[Publications] T.Matsuno: "Mass Spectrometric Investigation of Structures of Intermediates in Acridine Chemiluminescence" J.Mass Spectrom.Soc.,Jpn.(in press). (1996)

[Publications] M.Isobe: "New Analysis Method for Protein Phosphatase Type 2A Inhibitors Using the Firefly Bioluminescence System" Biosci.Biotech.Biochem.59. 2235-2238 (1995)

[Publications] M.Ohto: "Involvement of Ca^<2+>-signaling in the sugar-inducible expression of genes coding for sporamin and β-amylase of sweet potato" The Plant Journal. 7. 297-307 (1995)

[Publications] K.Teranishi: "Efficient preparation of alkoxymethyl carbonates by using potassium carbonate,chloromethyl alkyl ethers and alcohols" Bull.Chem.Soc.Jpn.68. 309-314 (1995)

[Publications] K.Teranishi: "One-step synthesis of novel carbonate,alkoxymethyl carbonate,from alcohol and chloromethyl alkyl ether using silver carbonate" Synthesis. 176-180 (1995)

[Publications] K.Satake: "Rearrangement of Bicyclo[2.2.2]octa-2,5-diene and Bicyclo-[3.2.2]nona-6,8-diene under the Conditions of Bromination" Bull.Chem.Soc.Jpn.69(in press). (1996)

[Publications] H.Okamoto: "Characterization of a Longicyclic[2,2,2,2]conjugated π System in 1,4-Difluorobenzene-Naphthalene Biplanemer" Bull.Chem.Soc.Jpn.68. 3557-3562 (1995)

[Publications] M.Matsumoto: "Effect of allylic oxygen on the reaction pathways of singlet oxygenation:selective formation of 1,2-dioxetanes from 1-alkoxymethyl-2-aryl-1-tert-butyl-2-methoxyethylenes" Tetrahedron Lett.37(in press). (1996)

[Publications] M.Matsumoto: "Synthesis and chemiluminescence of 3-biphenylyl-4,4-diisopropyl-3-methoxy-1,2-dioxetanes" Heterocycles. 41. 2419 (1995)

[Publications] K.Usami: "Two Luminescent Intermediates of Coelenterazine Analog,peroxide and Dioxetanone,Prepared by Direct Photooxygenation at Low Temperature" Tetrahedron Lett.36. 8613-8616 (1995)

[Publications] K.Usami: "Chemiluminescent Characters of Hydroperoxide and Dioxetanone of Coelenterate Luciferin Analog Prepared by Low-Temperature Photooxygenation" Chem.Lett.(in press). (1996)

[Publications] M.-C.Rho: "Zooxanthellatoxin-A,a novel polyoxygenated long chain compound,activates rabbit platelets,mediated via Ca^<2+> influx followed by the release of thromboxane A2 in an external Ca^<2+>-dependent manner" Br.J.Pharmacol.1996 ((in press))

[Publications] H.Nakamura: "Synthesis of 5-and 3,5-Substituted 2-Amino-pyrazines by Pd Mediated Still Coupling" Synlett. 1277-1278 (1995)

[Publications] H.Nakamura: "Zooxanthellatoxin-A,a Potent Vasoconstrictive 62-membered Lactone from a Symbiotic Dinoflagellate" J.Am.Chem.Soc.117. 550-551 (1995)

[Publications] K.Teranishi: "Synthesis of a model for the functional part of photoprotein aequorin" Biosci.Biotech.Biochem.59. 104-107 (1995)

[Publications] M.Matsumoto: "Thermal stability and chemiluminescence of 3-alkoxy-3-aryl-4,4-diisopropyl-1,2-dioxetanes" J.Chem.Soc.,Chem.Commun.431-432 (1995)

[Publications] M.Kitamura: "A new highly sensitive chemiluminescent assay of alkaline phosphatase using lucigenin and its application to enzyme immunoassay" J.Biolumin.Chemilumin.10. 1-7 (1995)

[Publications] H.Sasamoto: "Chemiluminescent enzymatic assay for cholesterol in serum using lucigenin" Anal.Chim.Acta. 310. 347-353 (1995)

[Publications] H.Sasamoto: "Highly sensitive immunological assays for human chorionic gonadotropin and prostatic acid phosphate using phenacyl phosphate as chemiluminescent label" Anal.Chim.Acta. 309. 221-225 (1995)

[Publications] H.Sasamoto: "Chemiluminescent assay of alkaline phosphatase using phenacvl phosphate" Anal.Chim.Acta. 306. 161-165 (1995)

[Publications] A.Tsuji: "Recent advances of chemiluminescent and bioluminescent assay" Jpn.J.Electroph.39. 301-309 (1995)

[Publications] P.Prados: "Generation of an active intermediate during the storage of a peroxyoxalate chemi-luminescence reagent solution under the presence of strong carboxylic acids" Anal.Sci.11. 575-580 (1995)

[Publications] 中村英士: "有機化学からみた渦鞭毛藻" 藻類. 43. 23-30 (1995)

[Publications] 前田昌子: "化学発光エンザイムイムノアッセイの原理と実際" 日本臨床. 53. 2096-2099 (1995)

[Publications] A.Tsuji: "Nonisotopic Probing,Blotting and Sequencing" Academic Press Inc., 10 (1995)

前田侯子お茶の水女子大学, 理学部, 教授 (40017190)