In-insect synthesis of oxygen-doped molecular nanocarbons

• 成果类型: Article
• 署名作者: Usami, Atsushi; Kono, Hideya; Austen, Vic; Phung, Quan Manh; Shudo, Hiroki; Kato, Tomoki; Yamada, Hayato; Yagi, Akiko; Amaike, Kazuma; Fujimoto, Kazuhiro J.; Yanai, Takeshi; Itami, Kenichiro
• 署名单位: Nagoya University; Nagoya University; Nagoya University; Nagoya University; RIKEN; RIKEN
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-11132
• DOI: 10.1126/science.adp9384
• 发表日期: 2025-06-05
• 页码: 1055-1061
• 关键词: warped nanographene; cytochrome-p450; expression; enzymes; porphyrin; gene

摘要

Many functional molecules and materials have been produced with organic chemistry or with in vitro enzymatic approaches. Individual organisms, such as insects, have the potential to serve as natural reaction platforms in which high densities of multiple enzymes can perform new and complex reactions. We report an in-insect unnatural product synthesis that takes advantage of their xenobiotic metabolism. We selectively transform belt- and ring-shaped molecular nanocarbons into otherwise difficult-to-prepare derivatives in which oxygen atoms are inserted into aromatic rings. Cytochrome P450 variants are most likely the enzymes responsible for this reaction. Molecular dynamics simulations and quantum chemical calculations indicated a possible mode of substrate incorporation into the enzyme and an unconventional mechanism of direct oxygen insertion into carbon-carbon bonds.