Constitution and Control of Chemical Amplification Systems Triggered by Photoinduced Electron Transfer

2004 Fiscal Year Final Research Report Summary

• Project/Area Number: 15550032
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Mie University
• Principal Investigator: TAKAHASHI Yasutake Mie University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (70197185)
• Project Period (FY): 2003 – 2004
• Keywords: Endoperoxides / Dioxetane / Photoreaction / Sensitizer / Electron Transfer / Benzocyclobutenylidene

Research Abstract

Photoinduced SET oxidation and reduction of endoperoxides and dioxetanes result in their decomposition via chain process to generate singlet oxygen and chemiluminescence. In this study, synthesis of oligomeric endoperoxides and dioxetanes is examined in order to constitute electron-relay reaction systems. Also studied is the photoreaction and control of the systems.
Synthesis of polymethylnaphthelenes and diaryldoxetanes are performed. Triiodobenzene, ethynylbenzene, and phthalic acids are used to synthesize the above mentioned oligomers of linear, side-chained, and dendrimer types.
Photoinduced decomposition of the oligomeric peroxides results in extrusion of dioxygen. Product analysis suggests efficient generation of singlet oxygen. The yield of singlet oxygen was tentatively determined to be about 70% by using fluorescence spectrophotometry. However, the value lacks reproducibility. Quite recently, it is found that the spectrophotometer has poor optical design and unexpectedly diminished sensitivity of the detector. The spectrophotometer with modified optical design and new detector is used to investigate the effect of sensitizer and solvent on the yield of singlet oxygen production.

Research Products

• [Journal Article] Effect of phenyl substitution on the lifetime and product distribution of cyclobutylidene : preference change in the rearrangements via 1,2-carbon shift and 1,2-hydrogen shift (2006)
  • Author(s): Y.Takahashi
  • Journal Title: Tetrahedron Lett. 46(in press)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Effect of phenyl substitution on the lifetime and product distribution of cyclobutylidene : preference change in the rearrangements via 1,2-carbon shift and 1,2-hydrogen shift (2006)
  • Author(s): Yasutake Takahashi, Takuro Sakakibara, Makoto Inaba, Hideo Tomioka, Shiro Koseki, Kazuyoshi Fujimoto, Hiroaki Umeda
  • Journal Title: Tetrahedron Lett. (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Direct observation and kinetic characterization of o-quinodimethane and its radical cation variant generated in a photoinduced electron-transfer reaction of 1,2-bis(a-styryl)benzene (2005)
  • Author(s): H.Ikeda
  • Journal Title: Tetrahedron Lett. 46 Pages: 8415-8418
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Tetracyanoanthraquinodimethanes with a Chiral Amide Group : Preparation, Properties, and Charge-Transfer Photochirogenetic Reaction with 1,2-Dianisylacenaphthene-1,2-diol (2005)
  • Author(s): T.Suzuki
  • Journal Title: J.Org.Chem. 70 Pages: 5592-5598
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Tetracyanoanthraquinodimethanes with a Chiral Amide Group : Preparation, Properties, and Charge-Transfer Photochirogenetic Reaction with 1,2-Dianisylacenaphthene-1,2-diol (2005)
  • Author(s): T.Suzuki, K.Ichioka, H.Higuchi, H.Kawai, K.Fujiwara, M.Okita, T.Tsuji, Y.Takahashi
  • Journal Title: J.Org.Chem. 70 Pages: 5592-5598
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Direct observation and kinetic characterization of o-quinodimethane and its radical cation variant generated in a photoinduced electron-transfer reaction of 1,2-bis(a-styryl) benzene (2005)
  • Author(s): H.Ikeda, T.Ikeda, M.Akagi, H.Namai, T.Miyashi, Y.Takahashi, M.Kamata
  • Journal Title: Tetrahedron Lett. 46 Pages: 1831-1835
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Intermediacy of Cyclobutylidene in Photochemical Methylenecyclo-propane Rearrangement (2005)
  • Author(s): Yasutake Takahashi, Yoko Mori, Akiko Nakamura, Hideo Tomioka
  • Journal Title: Tetrahedron Lett. 46 Pages: 8415-8418
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] X-ray Crystal Structure Study of Sterically Congested Diphenyldiazomethanes (2004)
  • Author(s): T.Iikubo
  • Journal Title: Eur.J.Org.Chem. 106 Pages: 3004-3010
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] X-ray Crystal Structure Study of Sterically Congested Diphenyldiazomethanes (2004)
  • Author(s): T.Iikubo, T.Ito, K.Hirai, Y.Takahashi, M.Kawano, Y.Ohashi, H.Tomioka
  • Journal Title: Eur.J.Org.Chem. Pages: 3004-3010
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron Transfer (2003)
  • Author(s): H.Ikeda
  • Journal Title: J. Am. Chem. Soc. 125 Pages: 9147-9153
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron Transfer (2003)
  • Author(s): H.Ikeda, K.Akiyama, Y.Takahashi, T.Nakamura, S.Ishizaki, Y.Shiratori, H.Ohaku, J.L.Goodman, A.Houman, D.D.M.Wayner, S.Tero-Kubota, T.Miyashi
  • Journal Title: J.Am.Chem.soc. 125 Pages: 9147-9157
  • Description: 「研究成果報告書概要(欧文)」より