A visible-light activated [2+2] cycloaddition reaction enables pinpointing carbon-carbon double bonds in lipids

作者:Feng, GF (Feng, Guifang)[ 1 ] ; Hao, YH (Hao, Yanhong)[ 1 ] ; Wu, L (Wu, Liang)[ 1 ] ; Chen, SM (Chen, Suming)[ 1 ]

CHEMICAL SCIENCE

卷: 11 期: 27 页: 7244-7251

DOI: 10.1039/d0sc01149e

出版年: JUL 21 2020

摘要

The precise location of CC bonds in bioactive molecules is critical for a deep understanding of the relationship between their structures and biological roles. However, the traditional ultraviolet light-based approaches exhibited great limitations. Here, we discovered a new type of visible-light activated [2 + 2] cycloaddition of carbonyl with CC bonds. We found that carbonyl in anthraquinone showed great reactivities towards CC bonds in lipids to form oxetanes under the irradiation of visible-light. Combined with tandem mass spectrometry, this site-specific dissociation of oxetane enabled precisely locating the CC bonds in various kinds of monounsaturated and polyunsaturated lipids. The proof-of-concept applicability of this new type of [2 + 2] photocycloaddition was validated in the global identification of unsaturated lipids in a complex human serum sample. 86 monounsaturated and polyunsaturated lipids were identified with definitive positions of CC bonds, including phospholipids and fatty acids even with up to 6 CC bonds. This study provides new insights into both the photocycloaddition reactions and the structural lipidomics.

关键词

KeyWords Plus:LINOLEIC-ACID ISOMERS; MASS-SPECTROMETRY; LOCATION ISOMERS; FATTY-ACIDS; LIPIDOMICS; POSITION; BENZOPHENONE; DISSOCIATION; IONIZATION; OZONOLYSIS

作者信息

通讯作者地址:

Wuhan University Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China.

通讯作者地址: Chen, SM (通讯作者)

Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China.

地址:

[ 1 ]‎ Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China

电子邮件地址:sm.chen@whu.edu.cn