Analysis of elementary process for chemi-excitation of CIEEL type dioxetanes by the use of photo-induced ionization in MALDI

2015 Fiscal Year Final Research Report

• Project/Area Number: 25410057
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kanagawa University
• Principal Investigator: Ijuin Hisako 神奈川大学, 付置研究所, 研究員 (60398948)
• Co-Investigator(Kenkyū-buntansha): Masakatsu Matsumoto 神奈川大学, 光機能性材料研究所, プロジェクト研究員 (10260986)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Keywords: 化学発光 / MALDI法質量分析 / ジオキセタン / ラジカルイオン種 / 電子移動

Outline of Final Research Achievements

CIEEL active dioxetanes bearing an aromatic electron donor display chemiluminescence by CTID mechanism, in which CT occurs from the electron donor to dioxetane O-O to produce excited species. We have recently found that CTID occurred for dioxetanes bearing a hydroxyphenyl moiety substituted further with an aryl that acted as an antenna to capture an electron from a matrix in negative-mode MALDI-TOF-Mass. In this work, we found that a bicyclic dioxetane bearing a phenol with such antenna captured an electron from matrix to decompose a keto ester, in which the ketone moiety but not the aromatic ester was in the an excited state. On the other hand, a vibrationally excited keto ester formed by collision induced dissociation in MS/MS.
In the coure of such investigation of dioxetanes we found that a quinacridone derivative was useful as a new matrix under negative-mode. When a planar organic base such as phenazine is added to matrix the ionization efficiency is markedly improved.

Free Research Field

有機化学