Unraveling the complexity of the lipidome requires the development of novel approaches to facilitate structural identification and characterization of lipid species with isomer-level discrimination.Ultraviolet photodi...Unraveling the complexity of the lipidome requires the development of novel approaches to facilitate structural identification and characterization of lipid species with isomer-level discrimination.Ultraviolet photodissociation tandem mass spectrometry(UVPD MS/MS)is a promising tool for structure determination of lipids.The sensitivity of UVPD for lipid analysis however is.limited mainly due to weak absorption of UV photons bya C=C.Herein,a C=C site-specific derivatization,the Paterno-Bichi.(PB)reaction,was used to incorporate a chromophore to the C=C moiety in fatty acyls,leading to significantly improved UVPD eficiency and sensitivity for pinpointing C=C locations.The wavelength-dependent photodissociation of the PB products demonstrated 4-CF;-benzophenone as the best reagent for UVPD in terms of the efficiency of generating C=C diagnostic fragments and simplicity for C=C location assignments.We demonstrated the efectiveness of this approach for the shotgun profiling of C=C location isomers in diferent lipid classes from complex lipid extraclis,highlighting its potential to advancing the identification of the C=C bond locations in unsaturated lipids.展开更多
基金supported by the National Natural Science_Foundation.of China(Grant Nos.21627807,21904079,and 21722506)the China Postdoctoral Science Foundation(Grant No.2018M631441).
文摘Unraveling the complexity of the lipidome requires the development of novel approaches to facilitate structural identification and characterization of lipid species with isomer-level discrimination.Ultraviolet photodissociation tandem mass spectrometry(UVPD MS/MS)is a promising tool for structure determination of lipids.The sensitivity of UVPD for lipid analysis however is.limited mainly due to weak absorption of UV photons bya C=C.Herein,a C=C site-specific derivatization,the Paterno-Bichi.(PB)reaction,was used to incorporate a chromophore to the C=C moiety in fatty acyls,leading to significantly improved UVPD eficiency and sensitivity for pinpointing C=C locations.The wavelength-dependent photodissociation of the PB products demonstrated 4-CF;-benzophenone as the best reagent for UVPD in terms of the efficiency of generating C=C diagnostic fragments and simplicity for C=C location assignments.We demonstrated the efectiveness of this approach for the shotgun profiling of C=C location isomers in diferent lipid classes from complex lipid extraclis,highlighting its potential to advancing the identification of the C=C bond locations in unsaturated lipids.
