期刊
CHEMPLUSCHEM
卷 85, 期 9, 页码 1959-1963出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.202000338
关键词
bond dissociation; cancer photoimmunotherapy; density functional calculation; near-infrared dyes; radical anions; silicon phthalocyanine
资金
- Rakuten Medical Japan
- JST-PRESTO [JPMJPR15P5]
- JST-CREST [JPMJCR1902]
- JSPS KAKENHI [17H01188]
- Photo-excitonix Project in Hokkaido University
- Grants-in-Aid for Scientific Research [17H01188] Funding Source: KAKEN
Ligand release from IR700, a silicon phthalocyanine dye used in near-infrared (NIR) photoimmunotherapy, initiates cancer cell death after NIR absorption, although its photochemical mechanism has remained unclear. This theoretical study reveals that the direct Si-ligand dissociation by NIR light is difficult to activate because of the high dissociation energy even in excited states, i. e., >1.30 eV. Instead, irradiation generates the IR700 radical anion, leading to acid-base reactions with nearby water molecules (i. e., calculated pK(b) for the radical anion is 7.7) to produce hydrophobic ligand-released dyes. This suggests two possibilities: (1) water molecules participate in ligand release and (2) light is not required for Si-ligand dissociation as formation of the IR700 radical anion is sufficient. Experimental evidence confirmed possibility (1) by using O-18-labeled water as the solvent, while (2) is supported by the pH dependence of ligand exchange, providing a complete description of the Si-ligand bond dissociation mechanism.
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