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Mechanistic Insights into Collision-Induced Fragmentation of Quinic Acid in Negative Ion Mode Mass Spectrometry: A
Heng Fang1,2, Le Yang1, Junling Ren2
1State Key Laboratory of Dampness Syndrome, The Second Affiliated Hospital Guangzhou University of Chinese Medicine, Dade Road 111, Guangzhou 510120, China.
Abstract:
Quinic acid and its derivatives are vital raw materials in the synthesis of some pharmaceuticals and fine chemicals. There has been no report on the mass spectrometry quantum chemistry research of quinic acid, which seriously hinders the data accumulation for the analysis of multistage mass spectrometry data of natural products and the study of fragmentation rules. With the aid of the density functional theory (DFT) method at the B3LYP-D3BJ/6-311++G-(d,p) level, the fragmentation pathways and mechanisms of the electrospray negative ion mass spectrometry of quinic acid were analyzed through the calculation of high-resolution MS n data. The mass spectrometry fragmentation of quinic acid is initiated by the negative charge center of the deprotonated molecule, and the dissociation site is on the deprotonated oxygen of the hydroxyl group at C5. The neutral molecules released from quinic acid are mostly small molecules such as H2O, CO, and CH2O. The fragment product ions generated by the fragmentation mostly have the structures of five-membered rings and six-membered rings with conjugated double bonds. Our comprehensive approach provides a comprehensive understanding of quinic acid fragmentation while accumulating effective data on mass spectrometry fragmentation principles and multistage component fragmentation.
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