Development of a Proton Spin Network Fingerprint Library to Support Mass Spectrometry-Based Identification of Pharmacophore-Bearing Constituents in the Botanical Supplement .

(L.) Urban (Apiaceae) has been utilized for centuries in traditional medicine systems in Southeast Asia and Southern Africa, including Madagascar. Previous studies have reported evidence of the therapeutic potential of formulations in models of Alzheimer's Disease and other dementias. Caffeoylquinic acids (CQAs) have been identified to be among the pharmacologically relevant metabolites contributing to the botanical's cognitive enhancement and neuroprotective effects. Isomers of CQAs are, however, difficult to differentiate by commonly used LC-MS techniques, making the characterization, standardization, and batch-to-batch consistency of these formulations challenging. Individual CQAs have unique proton Spin Network Fingerprints (pSNFs) that can be used to distinguish between CQA regioisomers within complex extracts. This work describes the development of a CQA-focused pSNF library that can be used to complement LC-MS methods for the accurate metabolite identification and characterization of bioactive fractions and extracts. The isolation of two new ( and ) and four known (-) CQAs and CQA analogues from and their contribution to the pSNF library are also discussed herein.