Quality Evaluation of Decoction Pieces of Gardeniae Fructus Based on Qualitative Analysis of the HPLC Fingerprint and Triple-Q-TOF-MS/MS Combined with Quantitative Analysis of 12 Representative Components

Table 2

Identification of the common peaks in the fingerprint by triple-Q-TOF-MS/MS.

Peak no.	tR (min)	Formula	MS			MS/MS^c	Identification	Types of compounds	Reference
			Measured	Theoretical	Error (ppm)
1	15.330	C16H22O10	409.0910^a	409.0907	0.7	193.0510, 373.1151, 167.0721, 149.0610, 89.0316, 211.0601, 161.0742, 179.0558, 123.0463, 409.0873, 143.0383	Gardenoside	Iridoids	[30, 36, 37]
2	17.542	C16H24O11	391.1249^b	391.1246	0.8	391.1272, 185.0840, 167.0716, 229.0746, 119.0328, 89.0251, 211.0643, 149.0615, 179.0578, 123.0711	Shanzhiside^d	Iridoids
			427.1017^a	427.1013	1.0	391.1273, 89.0261, 167.0721, 185.0825, 229.0728
3	18.098	C16H22O10	409.0911^a	409.0907	1.0	373.1163, 149.0619, 211.0617, 167.0718, 123.0466, 119.0355, 409.0875, 89.0252, 193.0534	Geniposidic acid^d	Iridoids
4	19.248	C17H24O11	439.1023^a	439.1013	2.4	439.1033, 241.0684, 101.0240	DAAME^d	Iridoids
5	21.181	C17H24O11	439.1023^a	439.1013	2.4	439.1088, 241.0733, 403.1295	Gardenoside^d	Iridoids
6	21.668	C16H26O8	345.1562^b	345.1555	2.1	165.0915, 89.0249, 119.0343, 101.0267	Jasminoside D	Monocyclic monoterpenoids	[37]
			381.1333^a	381.1322	3.0	165.0935, 345.1577, 89.0264, 179.0570, 119.0368, 101.0260, 121.1039
7	22.668	C16H24O9	395.1114^a	395.1114	-0.1	359.1353, 197.0822	Ixoroside	Iridoids	[37]
8	23.743	C17H24O11	439.1025^a	439.1013	2.8	439.1056, 403.1332, 241.0704	SME^d	Iridoids
9	26.666	C16H26O8	381.1332^a	381.1322	2.7	381.1332	Jasminoside B^d	Monocyclic monoterpenoids
10	30.424	C16H18O9	389.0648^a	389.0645	0.5	191.0564, 353.0885	Chlorogenic acid^d	Organic acids
11	31.971	C23H34O15	585.1619^a	585.1592	4.7	585.1644, 225.0778, 549.1867, 123.0462, 101.0257, 207.0671	Genipin gentiobioside^d	Iridoids
12	36.838	C17H24O10	423.1076^a	423.1063	3.0	423.1095, 225.0760, 387.1288	Geniposide^d	Iridoids
13	42.163	C16H26O7	365.1387^a	365.1373	4.0	365.1405	Jasminoside A	Monocyclic monoterpenoids	[37]
14	43.103	C16H26O7	365.1386^a	365.1373	3.7	365.1385	Jasminoside E	Monocyclic monoterpenoids	[37]
15	53.572	C27H30O16	609.1482^b	609.1461	3.4	609.1525, 301.0359	Rutin^d	Flavonoids
			645.1250^a	645.1228	3.4	609.1501, 301.0366
16	55.917	C27H34O15	597.1855^b	597.1825	5.0	597.1923, 391.1285, 223.0633, 185.0825, 205.0521, 167.0717, 229.0734	6′-Trans-sinapoyl shanzhiside	Iridoids
			633.1619^a	633.1592	4.3	597.1881, 391.1260, 205.0511
17	56.908	C27H32O14	615.1511^a	615.1486	4.1	579.1770, 325.0927, 367.1043, 223.0612, 385.1151, 193.0505, 205.0506, 123.0451	6′-Trans-sinapoyl gardoside	Iridoids	[37]
18	59.556	C25H24O12	515.1215^b	515.1195	3.9	353.0910, 191.0579, 515.1277, 179.0348, 173.0443, 161.0227, 135.04738, 155.0361	3,4-Dicaffeoylquinic acid	Organic acids	[30, 37]
19	61.039	C32H40O17	695.2208^b	695.2193	2.2	695.2261, 469.1387, 163.0391, 145.0249, 123.0456, 367.1069, 225.0764, 663.2029,101.0252	6″-O-Trans-coumaroyl genipin gentiobioside	Iridoids	[36, 37]
20	61.814	C44H64O24	1011.3519^a	1011.3482	3.7	1011.3585, 651.2726, 327.1621, 975.3809, 283.1722	Crocin I^d	Crocins
21	63.359	C31H32O16	659.1647^b	659.1618	4.5	497.1325, 659.1672, 335.0767, 191.0555, 353.0892, 161.0458	3,4-Di-O-caffeoyl-5-O-(3-hydroxy-3-methylglutaroyl) quinic acid	Organic acids	[30, 37]
22	63.534	C27H36O12	587.1926^a	587.1901	4.3	521.2075, 533.2077, 551.2697, 551.2697, 205.0517, 367.1050, 223.0621, 587.1956, 165.0928, 179.0727, 385.1160	6′-O-Trans-sinapoyl jasminoside L	Monocyclic monoterpenoids	[37]
23	64.290	C21H34O11	497.1810^a	497.1795	3.0	497.1855, 461.2069, 167.1092, 329.0637, 293.0889	Jasminoside T	Monocyclic monoterpenoids	[37]
24	64.985	C28H34O14	593.1895^b	593.1876	3.2	593.1943, 205.0518, 223.0649, 225.0781, 367.1057, 207.0645, 123.0466, 101.0236	6′-O-Trans-sinapoyl geniposide	Iridoids	[36, 37]
			629.1668^a	629.1643	4.0	593.1936, 205.0511, 225.0773, 223.0627, 123.0457
25	65.278	C38H54O19	849.2978^a	849.2953	2.9	327.1615, 283.1723, 651.2701, 239.1815, 849.3028, 489.2166	Crocin II^d	Crocins
26	71.292	C27H36O11	571.1957^a	571.1952	0.9	535.2258, 325.0947, 265.0740, 223.0627, 205.0521, 385.1184, 221.0848	6′-O-Trans-sinapoyl jasminoside A	Monocyclic monoterpenoids	[37]
27	75.160	C44H64O24	1011.3509^a	1011.3482	2.7	1011.3556, 651.2711, 327.1611, 975.3767	13-cis-Crocin II	Crocins	[37]
28	75.958	C32H44O14	687.2437^a	687.2425	1.7	327.1608, 651.2707, 283.1704, 687.2467, 239.1814, 323.0971, 179.0566	Crocin II	Crocins	[37]

^aQuasi-molecular ion was [M+Cl]⁻. ^bQuasimolecular ion was [M-H]⁻. ^cSequencing according to the abundance. ^dConfirmed by comparison with reference substances.