TABLE 2

LC-DAD-IT-TOF-MS analysis of SSa and its observed metabolites in rat biosamples

No.	T_R	UV	Positive MS¹	Negative MS¹	Positive MSⁿ	Negative MSⁿ	Identity
	min	nm
M0	39.9	<190	437.3402^{^a}, 455.3534, 583.3982, 601.4083,745.4511, 763.4635,803.4572, 819.4267	779.4593, 815.4310, 825.4654^a_, 842.4867, 893.4467	[763.4635] → 745.4532, 601.4123, 583.3985, 455.3514, 437.3403^a, 419.3329	[825.4654] → [779.4566^a]→ [617.4067^a] → 541.3513, 471.3464^a, 439.3207	SSa^{^b}
M0	39.9	<190		779.4593, 815.4310, 825.4654^a_, 842.4867, 893.4467	[455.3534] → 437.3398, 425.3399, 419.3295, 407.3296, 401.3224, 389.3199, 299.2361, 285.2213, 283.2049, 267.2123, 265.1946, 253.1961, 251.1805, 241.1945, 239.1811, 233.1897, 231.1755, 223.1689, 215.1789, 213.1648, 205.1584, 201.1634, 187.1484^a
M13	22.9	<190	821.4632	797.4706		[797.4706] → [635.4135^a] → 559.3655, 471.3479^a, 439.3214	HOSS^{^c}
M13	22.9	<190	821.4632	843.4772^a		[797.4706] → [635.4135^a] → 559.3655, 471.3479^a, 439.3214
M14	15.2	<190	819.4527	795.4561		[795.4561] → [633.3976^a] → 557.3457, 487.3436^a, 455.3172	Monooxidation of SSa
M14	15.2	<190	819.4527	841.4623^a		[795.4561] → [633.3976^a] → 557.3457, 487.3436^a, 455.3172	Monooxidation of SSa
M15	23.3	<190	819.4512	795.4553		[795.4553] → [633.3995^a] → 487.3436^a	Monooxidation of SSa
M15	23.3	<190	819.4512	841.4609^a		[795.4553] → [633.3995^a] → 487.3436^a	Monooxidation of SSa
M1	45.5	<190	437.3425^a	617.4076	[455.3541] → 285.2224, 267.2106, 223.1687, 205.1587, 187.1478^a	[617.4076^a] → 541.3523, 471.3485^a, 439.3222	PSGf^c
M1	45.5	<190	455.3541, 601.4077	663.4124^a		[617.4076^a] → 541.3523, 471.3485^a, 439.3222
M16	16.5	<190	657.3997	633.4018		[633.4018] → 557.3489, 487.3447^a, 455.3178	Monooxidation of PSGf
M16	16.5	<190	657.3997	679.4031^a		[633.4018] → 557.3489, 487.3447^a, 455.3178	Monooxidation of PSGf
M17	24.5	<190	657.3968	633.4029		[633.4029] → 487.3440^a, 455.3144	Monooxidation of PSGf
M17	24.5	<190	657.3968	679.4047^a		[633.4029] → 487.3440^a, 455.3144	Monooxidation of PSGf
M2	48.3	<190	437.3411^a, 455.3527	517.3513^a	[455.3527] → 285.2210, 267.2118, 223.1703, 205.1597, 187.1497^a		SGf^c
M2	48.3	<190	437.3411^a, 455.3527	517.3513^a
M3	52.3	<190	435.3271^a		[453.3378] → 423.3273^a, 393.3140, 285.2207, 267.2109, 233.1896, 221.1550, 215.1792, 203.1428, 175.1479		Δ¹-SGf
M3	52.3	<190	453.3378, 493.3279
M4	53.7	<190	435.3254^a, 453.3372		[453.3372] → 285.2217, 267.2114, 221.1536, 203.1443^a, 185.1335		3-keto-SGf
M5	18.6	<190	453.3369^a, 471.3457	533.3499^a	[471.3457] → 249.1861, 231.1739, 223.1697, 213.1651, 205.1601, 187.1489^a		Hydroxylation of SGf
M6	26.0	<190	453.3361^a, 471.3469	533.3467^a	[471.3469] → 453.3387^a		Hydroxylation of SGf
M6	26.0	<190	453.3361^a, 471.3469	533.3467^a	[453.3361] → 229.1584, 223.1693, 211.1477, 205.1591, 187.1487^a		Hydroxylation of SGf
M7	18.4	<190	467.3153^a, 485.3250	501.3234^a	[485.3250] → 455.3161, 263.1656, 245.1533, 231.1374, 223.1692, 205.1594, 199.1493, 187.1482^a	[501.3234] → 453.2987^a, 437.3038	SGf-27-oic acid
M8	42.2	<190	467.3167^a, 485.3273	501.3238^a	[485.3273] → 253.1451, 235.1340, 233.1907, 217.1224, 215.1805, 171.1169^a	[501.3238] → 453.2991^a, 437.3044	Carboxylation and hydroxylation of SGf
M9	27.0	<190	467.3158^a, 485.3259	501.3217^a	[485.3259] → 467.3140^a	[501.3217] → 453.3016^a, 437.3069	Unidentified
M9	27.0	<190	467.3158^a, 485.3259	501.3217^a	[467.3158] → 449.3050^a, 431.2941	[501.3217] → 453.3016^a, 437.3069
M10	14.7	<190	483.3098^a, 501.3199	517.3171^a	[501.3199] → 253.1447, 249.1867, 235.1345, 231.1743, 217.1235, 213.1635, 171.1167^a	[517.3171] → 469.2965^a, 453.3023	Carboxylation and hydroxylation of SGf
M11	19.6	<190	483.3104^a, 501.3204	517.3152^a	[501.3199] → 483.3127^a	[517.3152] → 469.2932^a, 453.2989	Unidentified
M11	19.6	<190	483.3104^a, 501.3204	517.3152^a	[483.3104] → 465.3021^a	[517.3152] → 469.2932^a, 453.2989
M12	30.2	<190	483.3123^a, 501.3207	517.3184^a	[501.3207] → 483.3087^a	[517.3184] → 469.2936^a, 453.2991	Unidentified
M12	30.2	<190	483.3123^a, 501.3207	517.3184^a	[483.3123] → 465.2983^a	[517.3184] → 469.2936^a, 453.2991

HOSS, hydroxysaikosaponin; LC-DAD-IT-TOF-MS, liquid chromatography–diode array detector coupled with hybrid ion trap–time-of-flight mass spectrometry; PSGf, prosaikogenin f; SGf, saikogenin f; SSa, saikosaponin a.
↵^a Of 100% relative signal intensity.
↵^b With standard.
↵^c With data in reference.