Chemical Characterization and Metabolic Profiling of the Compounds in the Chinese Herbal Formula Li Chang Decoction by UPLC-QTOF/MS

Table 3

Prototype and metabolic components of LCD in rat serum, urine, and fecal samples.

Metabolites	Prototype	Component name	Formula	tR (min)	Serum	Urine	Feces
—	P1	Choline	C5H13NO	1.25	√	√	√
—	P2	Arginine	C6H14N4O2	1.21	√	—	√
—	P3	Asparagine	C4H8N2O3	1.24	—	—	—
—	P4	Fructose	C6H12O6	1.33	—	—	—
—	P5	Trigonelline	C7H7NO2	1.36	√	√	—
—	P6	Sucrose	C12H22O11	1.43	—	—	√
—	P7	Raffinose	C18H32O16	1.51	—	—	—
—	P8	Stachyose	C24H42O21	1.65	—	—	—
—	P9	L-Malic acid	C4H6O5	1.66	—	—	√
—	P10	Citric acid	C6H8O7	1.69	√	√	—
—	P11	Valine	C5H11NO2	1.69	√	√	√
—	P12	Adenine nucleoside	C10H13N5O4	1.76/3.20	√	—	√
—	P13	Chebulic acid	C14H12O11	1.80/2.27	—	—	—
—	P14	Verbascose	C30H52O26	2.00	—	—	—
—	P15	Isoleucine	C6H13NO2	2.07	√	√	√
—	P16	L-Pyroglutamic acid	C5H7NO3	2.41	√	√	—
—	P17	Uridine	C9H12N2O6	2.66	—	—	—
—	P18	Succinic acid	C4H6O4	2.70	√	—	√
—	P19	p-Coumaric acid	C9H8O3	2.86	√	—	—
—	P20	Leucine	C6H13NO2	3.10	√	—	—
—	P21	Guanosine	C10H13N5O5	3.74	—	—	—
—	P22	Gastrodin	C13H18O7	3.85	—	√	—
—	P23	Gallic acid	C7H6O5	4.17	—	√	√
—	P24	Phenylalanine	C9H11NO2	5.12	√	√	√
—	P25	Codonopsine	C14H21NO4	6.27	—	—	√
—	P26	5-Galloylshikimic acid	C14H14O9	6.74	—	—	—
—	P27	3,4-Dihydroxybenzoic acid	C7H6O4	6.93	—	√	√
—	P28	Hamamelitannin	C20H20O14	7.95	—	—	—
—	P29	1,6-Di-O-galloyl-β-D-glucose	C20H20O14	8.52/8.91/9.09/9.25	—	—	—
—	P30	5-Hydroxyferulic acid	C10H10O5	8.99	√	√	—
—	P31	4-Hydroxybenzoic acid	C7H6O3	9.16	√	√	√
—	P32	Soyamaloside C	C23H32O16	9.61	√	—	—
—	P33	Brevifolincarboxylic acid	C13H8O8	9.73	—	—	—
—	P34	Chebulanin(1-O-galloyl-2,4-O-chebuloyl-b-D-Glc)	C27H24O19	9.98	—	—	—
—	P35	6,7-Dihydroxycoumarin	C9H6O4	10.04	—	—	√
—	P36	Corilagin	C27H22O18	10.18	—	—	—
—	P37	Quercetin 3-O-glucosyl-rutinoside	C33H40O21	10.37	—	—	√
—	P38	Euphormisin M3	C27H24O18	10.55	—	—	—
—	P39	Manghaslin	C33H40O20	10.58	—	—	—
—	P40	3,4,8,9,10-Pentahydroxydibenzo[b,d]pyran-6-one	C13H8O7	10.96	—	—	√
—	P41	Chebulagic acid	C41H30O27	11.05	—	—	—
—	P42	Typhaneoside	C34H42O20	11.25	—	—	√
—	P43	Rutin	C27H30O16	11.56	√	√	√
—	P44	Licuraside/liquiritin apioside	C26H30O13	11.65	—	√	√
—	P45	Hyperoside	C21H20O12	11.87	—	—	√
—	P46	Liquiritin	C21H22O9	11.85	√	√	√
—	P47	Dactylorhin A	C40H56O22	12.06	√	√	—
—	P48	Nicotiflorin	C27H30O15	12.18	√	—	√
—	P49	Isorhamnetin-3-O-rutinoside-7-O-rhamnoside	C34H40O20	12.23	—	—	—
—	P50	Narcissin	C28H32O16	12.27	√	√	√
—	P51	Vanillic acid	C8H8O4	12.60	√	√	—
—	P52	Isorhamnetin-3-O-beta-galactoside	C22H22O12	12.70	—	—	√
—	P53	Choerospodin	C21H22010	12.83	—	—	—
—	P54	Naringenin-7-O-glucoside	C21H22O10	12.95	—	—	—
—	P55	Notoginsenoside E	C48H82O20	12.96	√	√	√
—	P56	Gymnoside III	C42H58O23	13.22	—	—	—
—	P57	Lobetyolin	C20H28O8	13.24	—	√	—
—	P58	Ginsenoside Re	C48H82O18	13.34	√	—	—
—	P59	Ginsenoside Rg1	C42H72O14	13.40	√	—	√
—	P60	Violanthin	C27H30O14	13.65	—	√	√
—	P61	Militarine	C34H46O17	13.65	√	—	—
—	P62	Ononin/Ononin isomer	C22H22O9	13.73	—	—	—
—	P63	Licorice glycoside B/D1	C35H36O15	13.73	—	—	—
—	P64	Licorice glycoside C2	C36H38O16	13.81	—	—	—
—	P65	N, N′-diferuloylputrescine	C24H28N2O6	14.17	—	—	√
—	P66	Licorice glycoside E	C35H35NO14	14.34	—	—	—
—	P67	Pallidiflorin	C16H12O4	14.42	—	√	—
—	P68	Decanedioic acid	C10H18O4	14.45	√	√	√
—	P69	Isoliquiritigenin	C15H12O4	14.46	—	√	√
—	P70	Quercetin	C15H10O7	14.67	—	—	√
—	P71	Licorice saponin A3	C48H72O21	14.69	√	√	—
—	P72	Ginsenoside Rb1	C54H92O23	15.13	√	√	√
—	P73	Licorice saponin G2	C42H62O17	15.24	—	√	—
—	P74	Notoginsenoside R2	C41H70O13	15.31	—	—	√
—	P75	Naringenin	C15H12O5	15.57	—	—	—
—	P76	20S-Ginsenoside Rh1	C36H62O9	15.71	—	—	—
—	P77	Ginsenoside Rh4/Rk3	C36H60O8	15.76	—	—	—
—	P78	Licorice saponin G2 isomer	C42H62O17	15.83	—	—	—
—	P79	Isorhamnetin	C16H12O7	15.95	—	—	—
—	P80	Raho glycyrrhizin	C48H72O20	15.96	—	—	—
—	P81	Betulin	C30H50O2	16.10	—	—	—
—	P82	Ginsenoside Rd	C51H84O21	16.11	—	—	—
—	P83	Yunganoside G1	C48H74O21	16.14	—	—	—
—	P84	Glycyrrhizic acid	C42H62O16	16.31	—	—	—
—	P85	Glycyrrhizic isomer /uralsaponin A/licorice saponin K2/licorice saponin H2	C42H62O16	16.82/17.02	—	—	—
—	P86	Kaikasaponin III	C48H78O17	17.15	—	—	—
—	P87	Uralsaponin C/licorice saponin J2	C42H64O16	17.22	—	—	—
—	P88	Kaikasaponin I	C42H68O13	17.73	—	—	—
—	P89	Paniculatumoside A/paniculatumoside B	C28H40O9	18.00	—	—	—
—	P90	Glyasperin C	C21H24O5	18.09	—	—	—
—	P91	Ginsenoside F2	C42H72O13	18.57	—	—	—
—	P92	Atractylenolide III	C15H20O3	18.62	—	—	—
—	P93	Sophoraisoflavone A/semilicoisoflavone B	C20H16O6	19.91	—	—	—
—	P94	7-[4-(11-Hydroxy-undecyloxy)-phenyl]-7-pyridin-3-yl-hept-6-enoic acid ethyl ester	C31H45NO4	20.82	√	—	√
Total of prototypes					29	27	34
Metabolites	Prototype	Biotransformation	Formula	tR (min)	Serum	Urine	Feces
M1	P65	Loss of C14H17NO3 + oxidation	C10H11NO4	7.92	—	√	—
M2	P65	Loss of C14H17NO3 + internal hydrolysis	C10H13NO4	10.26	—	√	—
M3	P68	Desaturation	C10H16O4	15.84	—	√	—
M4	P68	Loss of O	C10H18O3	15.32	—	√	—
M5	P68	Loss of O + hydrogenation	C10H20O3	16.94	√	—	—
M6	P65	Loss of C14H18N2O3 + ketone formation	C10H8O4	12.16	—	√	—
M7	P27	Loss of O + glucuronidation	C13H14O9	10.48	—	√	—
	P31	Glucuronidation
M8	P47	Loss of C27H38O16 + ketone formation	C13H16O7	11.22	√	√	—
M9	P47	Loss of C27H38O16 and O	C13H18O5	15.34	—	√	—
M10	P28	Loss of O and C7H4O5 + hydrogenation	C13H18O8	8.74	—	√	—
	P47	Loss of C27H38O15 + oxidation
M11	P25	Loss of CH2	C13H19NO4	6.13	—	√	—
M12	P25	Loss of CH2 + sulfate conjugation	C13H19NO7S	9.85	—	√	—
M13	P63	Loss of C26H28O13 + glutamine conjugation	C14H16N2O4	13.77	—	√	—
M14	P63	Loss of C21H20O9 and O	C14H16O5	13.34	—	√	—
M15	P63	Loss of C21H20O8	C14H16O7	12.21	—	√	—
	P26	Loss of O and O + hydrogenation
M16	P63	Loss of C21H20O8 + oxidation	C14H16O8	8.21	—	√	—
M17	P63	Loss of C21H20O8 + oxidation	C14H16O8	9.28	—	√	—
M18	P65	Loss of C10H9NO3 + demethylation to carboxylic acid	C14H17NO5	8.16	—	√	—
M19	P28	Loss of C7H4O4+methylation	C14H18O10	4.85	—	√	—
M20	—P28	Loss of C7H4O4 + methylation	C14H18O10	5.12	—	√	—
M21	—P28	Loss of O and C7H4O5 + methylation	C14H18O8	7.3	—	√	—
	P63	Loss of C21H20O8 + internal hydrolysis
M22	P28	Loss of O and C7H4O5 + methylation	C14H18O8	11.29	—	√	—
	P63	Loss of C21H20O8 + internal hydrolysis
M23	P65	Loss of C10H9NO3	C14H19NO3	15.44	—	√	—
M24	P65	Loss of C10H9NO3	C14H19NO3	15.73	—	√	—
M25	P25	Desaturation	C14H19NO4	14.65	—	√	—
M26	P65	Loss of C10H8O3	C14H20N2O3	7.03	—	√	—
M27	P65	Loss of C10H8O3 + phosphorylation	C14H21N2O6P	5.86	—	√	—
M28	P25	Oxidation	C14H21NO5	2.32	—	—	√
M29	P25	Sulfate conjugation	C14H21NO7S	12.22	—	√	—
M30	P25	Phosphorylation	C14H22NO7P	10.82	—	√	—
M31	P43	Loss of C12H20O9	C15H10O7	14.63	—	√	√
M32	P44	Loss of C11H18O9	C15H12O4	14.47	—	√	√
	P63	Loss of C20H24O11
M33	P63	Loss of C20H24O11 + oxidation	C15H12O5	15.52	—	√	—
M34	P63	Loss of C20H24O12 + internal hydrolysis	C15H14O4	16.12	—	√	√
M35	P25	Methylation	C15H23NO4	14.47	—	√	—
M36	P47	Loss of C13H16O7 and C13H16O6 + methylation	C15H26O9	13.24	—	√	—
M37	P43	Loss of C12H20O10 and O + methylation	C16H12O5	18.12	—	√	—
M38	P65	Loss of C14H18N2O3 + glucose conjugation	C16H20O8	13.53	—	√	—
M39	P63	Loss of C15H10O4 + internal hydrolysis	C20H28O12	8.03	—	√	—
M40	P43	Loss of C6H10O4 + oxidation	C21H20O13	9.06	—	√	—
M41	P28	Loss of O and O + methylation	C21H22O12	8.03	—	√	—
M42	P63	Loss of C9H6O2 + glucuronidation	C32H38O19	9.94	—	√	—
M43	P59	Loss of O	C42H72O13	15.11	√	√	√
M44	P27	Loss of O and O	C7H6O2	12.52	—	√	—
	P31	Loss of O
M45	P23	Loss of O and O	C7H6O3	13.51	√	√	—
	P27	Loss of O
	P28	Loss of O and C13H14O10
	P47	Loss of C27H38O15 and C6H10O6 + demethylation to carboxylic acid
M46	P23	Loss of O	C7H6O4	9.12	—	√	—
	P28	Loss of C13H14O10
	P31	Oxidation
M47	P27	Oxidation	C7H6O5	4.16	—	√	√
	P28	Loss of C13H14O9
M48	P27	Loss of O + sulfate conjugation	C7H6O6S	6.83	√	√	—
	P31	Sulfate conjugation
M49	P23	Loss of O + sulfate conjugation	C7H6O7S	6.76	√	√	—
	P36	Loss of C20H16O14 + sulfate conjugation
	P27	Sulfate conjugation
M50	P27	Loss of O and O + hydrogenation	C7H8O2	8.01	—	√	√
	P31	Loss of O + hydrogenation
	P47	Loss of C27H38O15 and C6H10O5
M51	P27	Loss of O and O + methylation	C8H8O2	11.44	—	√	—
	P31	Loss of O + methylation
M52	P36	Loss of C20H16O14 and O + methylation	C8H8O3	13.29	—	√	—
	P26	Loss of C7H8O5 and O + methylation
	P23	Loss of O and O + methylation
	P27	Loss of O + methylation
	P31	Methylation
M53	P23	Loss of O + methylation	C8H8O4	12.58	√	√	—
	P27	Methylation
	P36	Loss of C20H16O14 + methylation
	P28	Loss of C13H14O10 + methylation
M54	P23	Methylation	C8H8O5	8.53	√	√	√
	P36	Loss of C20H16O13 + methylation
	P26	Loss of C7H8O4 + methylation
	P28	Loss of C13H14O9 + methylation
M55	P63	Loss of C26H28O13 + internal hydrolysis	C9H10O3	9	√	√	—
M56	P63	Loss of C26H28O12	C9H8O3	11.56	√	√	√
	P65	Loss of CH2 and C14H18N2O3
M57	P63	Loss of C26H28O12 + oxidation	C9H8O4	14.04	—	—	√
M58	P63	Loss of C26H28O12 + oxidation	C9H8O4	9.04	—	√	—
M59	P50	Glucuronidation	C34H40O22	10.68	—	√	—
M60	P37	Ketone formation	C33H38O22	9.37	—	√	—
	P43	Glucuronidation
M61	P47	Loss of C13H16O7 and O + phosphorylation	C27H41O17P	5.05	—	√	—
M62	P50	Demethylation to carboxylic acid	C28H30O18	10.57	—	√	—
M63	P59	Loss of C6H10O6	C36H62O8	21.05	—	—	√
	P58	Loss of C12H20O10
M64	P37	Loss of O and C6H10O6 + hydrogenation	C27H32O14	13.05	—	—	√
	P43	Loss of O and O + hydrogenation
M65	P50	Loss of C6H10O5 + demethylation to carboxylic acid	C22H20O13	10.6	—	√	—
M66	P84	Loss of C12H16O12 + oxidation	C30H46O5	19.88	—	—	√
	P71	Loss of C12H16O12 and C6H10O5 + oxidation
M67	P84	Loss of C12H16O12 + oxidation	C30H46O5	19.47	√	—	√
	P71	Loss of C12H16O12 and C6H10O5 + oxidation
M68	P50	Loss of C6H10O4	C22H22O12	13.16	√	√	—
	P37	Loss of C12H20O9 + methylation
	P43	Loss of C6H10O4 + methylation
M69	P37	Loss of C12H20O10 + demethylation to carboxylic acid	C21H18O13	13.13	√	√	—
	P43	Loss of C6H10O5 + demethylation to carboxylic acid
M70	P50	Loss of C6H10O4 and O + ketone formation	C22H20O12	12.83	—	√	—
M71	P50	Loss of C6H10O4 and O + ketone formation	C22H20O12	12.51	—	√	—
M72	P84	Loss of C12H16O12	C30H46O4	22.29	√	—	—
	P71	Loss of C12H16O12 and C6H10O5
M73	P84	Loss of C12H16O13 + ketone formation	C30H44O4	19.47	√	√	√
M74	P50	Loss of C6H10O5	C22H22O11	15.04	—	√	—
	P37	Loss of C12H20O10 + methylation
	P43	Loss of C6H10O5 + methylation
M75	P50	Loss of C6H10O5 + demethylation and methylene to ketone	C21H18O12	13.1	—	√	—
	P37	Loss of C12H20O10 + ketone formation
	P43	Loss of C6H10O5 + ketone formation
M76	P50	Loss of C6H10O5 + demethylation and methylene to ketone	C21H18O12	12.79	—	√	—
	P37	Loss of C12H20O10 + ketone formation
	P43	Loss of C6H10O5 + ketone formation
M77	P50	Loss of C6H10O4 and CH2O	C21H20O11	13.08	√	√	—
	P37	Loss of C12H20O10
	P43	Loss of C6H10O5
M78	P50	Loss of C6H10O4 and CH2O	C21H20O11	12.95	√	√	—
	P37	Loss of C12H20O10
	P43	Loss of C6H10O5
M79	P44	Loss of C5H8O4 + oxidation	C21H22O10	13.79	—	√	—
	P37	Loss of O and C12H20O10 + hydrogenation
	P43	Loss of C6H10O5 and O + hydrogenation
M80	P44	Loss of C5H8O5 + demethylation to carboxylic acid	C21H20O10	11.83	√	√	—
	P50	Loss of C6H10O5 and CH2O
	P37	Loss of O and C12H20O10
	P43	Loss of C6H10O5 and O
M81	P44	Loss of C5H8O5+ketone formation	C21H20O9	10.5	—	√	—
M82	P44	Loss of C5H8O5+hydrogenation	C21H24O8	13.18	—	√	—
M83	P6	Loss of H–2O + methylation	C13H26O10	3.74	—	√	—
M84	P47	Loss of C13H16O7 and C13H16O6 + demethylation and methylene to ketone	C13H20O10	7.5	—	√	—
M85	P58	Loss of C36H60O9 + methylation	C13H24O9	6.42	—	√	—
	P50	Loss of C16H10O7 + methylation
	P37	Loss of C21H18O12 + methylation
	P7	Loss of C6H10O6 and O + methylation
	P43	Loss of C15H8O7 + methylation
	P6	Loss of O and O + methylation
	P8	Loss of C6H10O6 and C6H10O6 + methylation
M86	P47	Loss of C27H38O15 + methylation	C14H20O7	11.44	—	√	—
	P74	Loss of C21H28O10 + methylation
M87	P50	Loss of C12H20O9 and CH2O	C15H10O6	13.08	—	√	—
	P37	Loss of C18H30O15
	P43	Loss of C12H20O10
M88	P47	Loss of C27H38O16	C13H18O6	10.65	—	√	√
	P74	Loss of C21H28O11
M89	P47	Loss of C27H38O16 + loss of hydroxymethylene	C12H16O5	11.17	—	√	—
	P74	Loss of C21H28O11 + loss of hydroxymethylene
M90	P44	Loss of C11H18O10	C15H12O3	10.5	—	√	—
M91	P12	Loss of O + loss of hydroxymethylene	C9H11N5O2	1.38	—	—	√
M92	P74	Loss of C13H16O6 and C13H16O6	C8H14O5	11.2	—	√	—
M93	P36	Loss of C20H16O13 + decarboxylation	C6H6O3	6	—	√	—
M94	P26	Loss of C7H4O5	C7H10O4	14.59	—	√	—
M95	P36	Loss of C20H16O14 + taurine conjugation	C9H11NO6S	2.81	√	—	—
M96	P36	Loss of C14H6O10 + demethylation and methylene to ketone	C12H12O9	4.71	—	√	—
M97	P23	Loss of O and O + glucose conjugation	C13H16O8	4.11	—	√	—
	P36	Loss of C14H6O10
	P26	Loss of C7H8O5 and O + glucose conjugation
	P31	Glucose conjugation
	P47	Loss of C27H38O16 + demethylation to carboxylic acid
M98	P36	Loss of C14H6O10 + hydrogenation	C13H18O8	8.74	—	√	—
M99	P36	Loss of C13H12O10	C14H10O8	13.63	—	√	—
M100	P23	Loss of O + glucose conjugation	C13H16O9	6.81	√	√	—
	P27	Glucose conjugation
	P28	Loss of C7H4O5
	P36	Loss of C14H6O9
	P26	Loss of C7H8O5 + glucose conjugation
M101	P23	Loss of O + glucose conjugation	C13H16O9	6.57	√	√	—
	P27	Glucose conjugation
	P28	Loss of C7H4O5
	P36	Loss of C14H6O9
	P26	Loss of C7H8O5 + glucose conjugation
M102	P23	Loss of O + glucuronidation	C13H14O10	5.69	—	√	—
	P26	Loss of C7H8O5 + glucuronidation
	P27	Glucuronidation
	P28	Loss of C7H4O5 + ketone formation
M103	P36	Loss of C14H6O9 + methylation	C14H18O9	3.63	—	√	—
M104	P13	Loss of H–2O + hydrogenation	C14H16O10	7.96	—	√	—
M105	P36	Loss of C13H12O8 + methylation	C15H12O10	11.93	—	√	—
M106	P36	Loss of C13H12O8 + methylation	C15H12O10	10.7	—	√	—
M107	P36	Loss of C13H12O9 + glutamine conjugation	C19H18N2O11	14.07	—	—	√
Total of metabolites					22	96	18