Four undescribed ginkgolides, including two rare sesquiterpene ginkgolides (compounds 1 and 2) and two diterpenoid ginkgolides (compounds 3 and 4), were isolated from Ginkgo biloba L. The structures of these four ginkgolides were identified based on extensive spectroscopic analysis, DP4+ probability analysis and X-ray diffraction. Compounds 1 and 2 exhibited excellent antiplatelet aggregation activities with IC50 values of 1.20 ± 0.25 and 4.11 ± 0.34 μM, respectively.

Four new ferulic acid sucrose esters, β-D-(1-O-acetyl-6-O-trans-feruloyl)fructofuranosyl-a-D-2\',6\'-O-diacetylglucopyranoside (1), β-D-(1-O-acetyl-6-O-trans-feruloyl)fructofuranosyl-a-D-2\',4\'-O-diacetylglucopyranoside (2), β-D-(6-O-trans-feruloyl)fructofuranosyl-a-D-2\',4\',6\'-O-triacetylglucopyranoside (3), β-D-(1-O-acetyl-6-O-trans-feruloyl)fructofuranosyl-a-D-4\',6\'-O-diacetylglucopyranoside (4), together with four known phenylpropanoids (5-8) were isolated from the rhizome of Sparganium stoloniferum (Graebn.) Buch.-Ham. ex Juz. Their structures were elucidated by chemical evidence and spectral analysis. Compounds 1-8 exhibited obvious inhibitory effects on ADP-induced platelet aggregation.

Ginkgolides are the most important bioactive components of Ginkgo biloba L, of which ginkgolide B has been successfully developed and marketed as a drug. The reported ginkgolides are very rare and exhibit a complex matrix due to the chemodiversity of Ginkgo biloba L. Herein, the global profile of characteristic ion and neutral loss recognition strategy were used for to discover eight undescribed ginkgolides, very rare cyclohexane ginkgolides R-V, ginkgolides D-F, and eight known ginkgolides. These ginkgolides were target isolated and identified using high-resolution mass spectrometry, nuclear magnetic resonance spectroscopy, and X-ray crystallography. The undescribed and known ginkgolides exhibited antiplatelet aggregation activities. In particular, compounds U and D had IC50 values of 2.20 ± 0.15 and 6.50 ± 0.87 μM, respectively. This study has enriched the known structural diversity of ginkgolides and extended the application of mass spectrometry to the global profiling of natural products present in Ginkgo biloba L. Moreover, it could help chemists rapidly discover unreported compounds from a complex matrix.