Table 4.

UPLC–MS/MS data-negative ion mode for acanthosessilioside G–O identified in ASFEx.

Acanthosessilioside	Molecular Formula	MW	Measured Value a [M–H]	MS/MS Fragmentation a
G	C42H66O15	810.44	809.2	647.2 [M–H–Glc]–; 587.2 [M–Glu–C2H3O2]–; 485.2 [M–H–Glc–Glc]–; 467.4 [M–H–Glc–Glc–H2O]–; 423.0 [M–H–Glc–Glc–HCOO–H2O]–; 405.4 [M–H–Glc–Glc–HCOO– 2H2O]–; 179.2 [M–H–Glu–3,4-seco-Triterpenoid–C2H3O2–2C3H5–H2O–HCOO]–; 161.2[M–H–3,4-seco-Triterpenoid–Glu–C2H3O2–2C3H5–2H2O-HCOO]–
H	C48H76O19	956.50	955.6	485.4 [M–H–Rha–Glc–Glc]–; 469.4 [M–H–Rha–Glc–Glc–H2O]–; 439.4 [M–H–Rha–Glc–Glc–HCOO]–; 423.4 [M–H–Rha–Glc–Glc–HCOO–H2O]–; 405.2 [M–H–Rha–Glc–Glc–HCOO–2H2O]–; 367.0 [M–H–Rha–Glc–Glc–HCOO–H2O–2C3H5]–; 325.0 [M–H–Rha-3,4-seco-Triterpenoid–C2H3O2–H2O–2C3H5–HCOO]–; 161.2 [M–H–Rha–Glu–3,4-seco-Triterpenoid – C2H3O2–H2O–2C3H5–HCOO]–
I	C49H78O19	970.51	969.6	808.0 [M–H–Rha]–; 499.4 [M–H–Rha–Glc–Glc]–; 469.2 [M–H–3,4-seco-Triterpenoid –C3H5O2–2C3H5–H2O–HCOO]–; 455.0 [M–H–Rha–Glc–Glc–HCOO]–; 365.4 [M–H–Rha–Glc–Glc–HCOO–C3H5O2–H2O]–; 325.0 [M–H–Rha–3,4-seco-Triterpenoid–C3H5O2–2C3H5–H2O–HCOO]–; 160.6 [M–H–Rha–Glu–3,4-seco-Triterpenoid–C3H5O2–2C3H5–2H2O–HCOO]–
J	C49H78O18	954.52	953.6	483.2 [M–H–Rha–Glc–Glc]–; 469.2 [M–H–Rha–Glc–Glc–H2O]–; 409.2 [M–H–Rha–Glc–Glc–HCOO–C3H6O2]–; 367.2 [M–H–Rha–Glc–Glc–HCOO–C3H6O2–C3H5]–; 323.4 [M–H–Rha–Glc–Glc–HCOO–C3H6O2–C3H5–HCOO]-; 160.8 [M–H–Rha–Glu–3,4-seco-Triterpenoid–C3H5O2–2C3H5–HCOO–H2O]–
K	C51H80O20	1012.52	1011.5	849.6 [M–H–Rha–H2O]–; 541.4 [M–H–Rha–Glc–Glc]–; 479.6 [M–H–Rha–Glu–Glu–HCOO–H2O]–; 469.2 [M–H–3,4-seco-Triterpenoid–HCOO]–; 454.8 [M–H–Rha–Glu–Glu–HCOO–C3H5]–; 405.4 [M–H–Rha–Glu–Glu–C2H2O2–C3H7O–H2O]–; 364.8 [M–H–Rha–Glu–Glu–C2H2O2–C3H7O–H2O–C3H5]–; 325.0 [M–H–Rha–Glu–Glu–C2H2O2–C3H7O–H2O–2C3H5]–; 160.8 [M–H–Rha–Glu–3,4-seco-Triterpenoid–C2H2O2–2H2O–2C3H5–C3H7O–HCOO]–
L	C49H78O19	970.51	969.6	499.4 [M–H–Rha–Glc–Glc]–; 469.2 [M–H–3,4-seco-Triterpenoid–HCOO]–; 323.0[M–H–Rha–3,4-seco-Triterpenoid–C3H5O2–C3H5–HCOO]–;160.8[M–H–Rha–Glu–3,4-seco-Triterpenoid–C3H5O2–C3H5–HCOO]–
M	C52H84O20	1028.56	1027.6	557.4 [M–H–Rha–Glc–Glc]–; 468.8 [M–H–3,4-seco-Triterpenoid]–; 367.2 [M–H–Rha–Glc–Glc–C3H6O2–C3H8O–C3H6]–; 323.2 [M–H–Rha–3,4-seco-Triterpenoid–C3H5O2–C3H7O–C3H5–H2O–HCOO]–; 161.2 [M–H–Rha–Glu–3,4-seco-Triterpenoid–C3H5O2–C3H7O–C3H5–H2O–HCOO]-
N	C49H78O21	1002.50	1001.6	531.2 [M–H–Rha–Glc–Glc]–; 486.8 [M–H–Rha–Glc–Glc–HCOO]–; 469.2[M–H–Rha–Glu–Glu–HCOO–2H2O]–; 437.2 [M–H–Rha–Glu–Glu–2H2O–C2H3O2]–; 393.4 [M–H–Rha–Glu–Glu–HCOO–H2O–C2H3O2]–; 379.4 [M–H–Rha–Glu–Glu–HCOO–2H2O–C3H5O2]–; 367.4 [M–H–Rha–3,4-seco-Triterpenoid–2H2O–C3H5O2]–; 325.2 [M–H–3,4-seco-Triterpenoid–2H2O–C3H5O2–HCOO–Rha]–; 161.0[M–H–Rha–Glu–3,4-seco-Triterpenoid–2H2O–C3H5O2–HCOO]–
O	C49H78O21	1002.50	1001.6	531.4 [M–H–Rha–Glc–Glc]–; 469.0 [M–H–3,4-seco-Triterpenoid–C3H5O2–2H2O–2C3H5]–; 437.4 [M–H–Rha–Glc–Glc–C2H3O2–2H2O]–; 379.2 [M–H–Rha–Glu–Glu–C3H5O2–2H2O–HCOO]–; 367.2[M–H–Rha–3,4-seco-Triterpenoid–C3H5O2–3H2O–2C3H5]–; 325.2[M–H–Rha–3,4-seco-Triterpenoid–C3H5O2–3H2O–2C3H5–HCOO]−; 161.2[M–H–Rha–Glu–3,4-seco-Triterpenoid–C3H5O2–4H2O–2C3H5–HCOO]–

^a Mass accuracy < 5 ppm.