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

光致电子转移引发的化学放大系统的构成与控制

• 批准号: 15550032
• 负责人: TAKAHASHI Yasutake
• 金额: $ 2.43万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550032/
• 关键词: Endoperoxides; Dioxetane; Photoreaction; Sensitizer; Electron Transfer; Benzocyclobutenylidene; 光誘起電子移動

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.

光诱导的SET氧化和内过氧化物和二氧乙烷的还原导致它们通过链式过程分解产生单线态氧和化学发光。本研究探讨了低聚内过氧化物和二氧乙烷的合成，以建立电子接力反应体系。研究了系统的光反应和控制。合成了聚甲基萘和二芳基十二烷。三碘苯、乙基苯和邻苯二甲酸可用于合成上述线性、侧链和树突状低聚物。光诱导低聚过氧化物的分解导致双氧的挤出。产品分析表明单线态氧的高效生成。用荧光分光光度法初步测定了单线态氧的产率约为70%。然而，该值缺乏可重复性。最近，人们发现，分光光度计有不良的光学设计和意想不到的降低灵敏度的探测器。采用改进光学设计的分光光度计和新型检测器，研究了增感剂和溶剂对单线态产氧收率的影响。

项目成果

X-ray Crystal Structure Study of Sterically Congested Diphenyl diazomethanes

空间拥挤二苯基重氮甲烷的 X 射线晶体结构研究

• 发表时间: 2004
• 期刊: Eur.J.Org.Chem.
• 作者: T.Iikubo;T.Ito;K.Hirai;Y.Takahashi;M.Kawano;Y.Ohashi;H.Tomioka;T.Ito et al.
• 通讯作者: T.Ito et al.

Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron Transfer

光致电子转移引发亚甲基环丙烷重排机理的光谱和量热研究

• 发表时间: 2003
• 期刊: J. Am. Chem. Soc. 125
• 作者: T.Iikubo;T.Ito;K.Hirai;Y.Takahashi;M.Kawano;Y.Ohashi;H.Tomioka;T.Ito et al.;H.Ikeda
• 通讯作者: H.Ikeda

Intermediacy of cyclobutylidene in photochemical methylenecyclopropane rearrangement

亚环丁烯在光化学亚甲基环丙烷重排中的中间作用

• DOI: 10.1016/j.tetlet.2005.09.149
• 发表时间: 2005
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Yasutake Takahashi;Y. Mori;A. Nakamura;H. Tomioka
• 通讯作者: H. Tomioka

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

1,2-双(a-苯乙烯基)苯光诱导电子转移反应中产生的邻醌二甲烷及其自由基阳离子变体的直接观察和动力学表征

• 发表时间: 2005
• 期刊: Tetrahedron Lett. 46
• 作者: Yasutake Takahashi;Takuro Sakakibara;Makoto Inaba;Hideo Tomioka;Shiro Koseki;Kazuyoshi Fujimoto;Hiroaki Umeda;H.Ikeda
• 通讯作者: H.Ikeda

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

苯基取代对环丁叉寿命和产物分布的影响：通过 1,2-碳转移和 1,2-氢转移重排的偏好变化

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 46(in press)
• 作者: Y.Takahashi