Investigation of Isomeric Transformations of Chlorogenic Acid in Buffers and Biological Matrixes by Ultraperformance Liquid Chromatography Coupled with Hybrid Quadrupole/Ion Mobility/Orthogonal Acceleration Time-of-Flight Mass Spectrometry

Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203, PR China.
Journal of Agricultural and Food Chemistry (Impact Factor: 2.91). 09/2011; 59(20):11078-87. DOI: 10.1021/jf203104k
Source: PubMed


Ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (UPLC-IM-MS) was used to study the isomeric transformations of trans-5-caffeoylquinic acid, an extremely active compound present in multiple vegetables, fruits, and beverages. The UPLC/oa-TOF MS results proved that in phosphate buffer (pH 7.4), plasma, or urine sample, trans-5-caffeoylquinic acid first isomerizes to trans-4-caffeoylquinic acid and then to trans-3-caffeoylquinic acid by intramolecular acyl migration. When exposed to UV light, trans-3-, -4-, and -5-caffeoylquinic acids undergo cis/trans isomerization to form cis isomers. The isomerization was solely dependent on the pH of the matrix, as well as the incubation temperature, and was independent of metabolic enzymes. UPLC-IM-MS results revealed that a reversible cis/trans isomerization of caffeoylquinic acids could also be induced by the electric field in an electrospray source. Thus, understanding the possible role of electric field-induced isomerization of caffeoylquinic acids may help lessen the confusion between gas phase phenomena and liquid state chemistry when applying IM-MS analysis. The comprehensive understanding of caffeoylquinic acid isomerization transformations is crucial for the appropriate handling of samples and interpretation of experimental data.

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    • "The metabolites of 5-CQA containing acyl groups were expected to follow the same isomerization. According to previous reports and our experience (Clifford et al., 2003; Xie et al., 2011a), the acyl isomers of 5-CQA and its metabolites can be distinguished by their chromatographic and characteristic MS fragmentation behaviors. "
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