Investigation of the Chemical Changes from Crude and Processed Paeoniae Radix Alba-Atractylodis Macrocephalae Rhizoma Herbal Pair Extracts by Using Q Exactive High-Performance Benchtop Quadrupole-Orbitrap LC-MS/MS

Table 1

Major chemical constituents identified in crude and processed Paeoniae Radix Alba and in crude and processed Paeoniae Radix Alba-Atractylodis Macrocephalae Rhizoma herbal pair.

No.	𝑡𝑅 (min)	Compound name	Formula	Paeoniae; Radix Alba		Paeoniae Radix Alba-Atractylodis Macrocephalae Rhizoma herbal pair
				(Measured area)		(Measured area)
				Crude	Processed	Crude	Processed
1	0.84	6-O-galloylsucrose	C19H26O15	1.8570𝐸+08	1.9012𝐸+08	4.2870𝐸+07	4.4158𝐸+07
2	0.84	Glucogallin	C13H16O10	2.9739𝐸+08	2.5698𝐸+08	1.0931𝐸+08	—
3	1.05	Desbenzoylpaeoniflorin	C16H24O10	1.6682𝐸+08	1.6263𝐸+08	9.8500𝐸+07	—
4	1.06	1′-O-galloylsucrose	C19H26O15	3.2574𝐸+08	2.9123𝐸+08	—	—
5	1.07	1-O-glucopyranosyl paeonisuffrone	C16H24O9	2.8667𝐸+08	2.3654𝐸+08	1.1532𝐸+08	—
6	1.13	Gallic acid	C7H6O5	4.1152𝐸+09	4.0736𝐸+09	2.7186𝐸+09	3.1711𝐸+09
7	1.18	Oxypaeoniflorin sulfonate	C23H28O14S	4.9527𝐸+07	3.5407𝐸+07	6.1568𝐸+06	8.5010𝐸+07
8	1.22	Ethyl gallate	C9H10O5	5.1351𝐸+07	6.7200𝐸+07	1.5592𝐸+07	4.8337𝐸+07
9	1.22	6-O-galloyl desbenzoylpaeoniflorin	C23H28O14	9.9020𝐸+07	9.5040𝐸+07	5.3798𝐸+07	—
10	1.26	6-O-glucopyranosyl-lactinolide	C16H26O9	1.0875𝐸+08	1.1180𝐸+08	—	3.7130𝐸+07
11	1.30	Paeoniflorin sulfonate I	C23H28O13S	5.3777𝐸+07	3.6391𝐸+07	7.3077𝐸+06	7.7185𝐸+07
12	1.30	Mudanpioside E sulfonate	C24H30O15S	5.3777𝐸+07	3.6391𝐸+07	7.3077𝐸+06	7.7185𝐸+07
13	1.43	6-O-glucopyranosyl-lactinolide	C16H26O9	7.4342𝐸+08	6.5904𝐸+08	4.0712𝐸+08	3.1407𝐸+08
14	1.64	Mudanpioside F	C16H24O8	6.4178𝐸+08	6.0980𝐸+08	4.0130𝐸+08	6.6680𝐸+07
15	1.76	Isomaltopaeoniflorin sulfonate	C29H38O18S	1.8858𝐸+09	1.1382𝐸+09	2.6277𝐸+08	5.8622𝐸+07
16	1.81	Pedunculagin	C34H24O22	4.8098𝐸+07	—	5.6076𝐸+07	1.2660𝐸+09
17	1.97	Paeoniflorin sulfonate I	C23H28O13S	3.1881𝐸+10	2.3387𝐸+10	6.6202𝐸+09	5.5241𝐸+10
18	2.25	Oxypaeoniflorin	C23H28O12	2.3173𝐸+09	2.4115𝐸+09	1.6734𝐸+09	1.4513𝐸+09
19	2.36	Gallotannin	C27H24O18	2.2850𝐸+08	2.2458𝐸+08	1.6284𝐸+08	1.6703𝐸+08
20	2.37	1-O-benzoylsucrose	C19H26O12	1.3761𝐸+08	1.3161𝐸+08	1.1673𝐸+08	8.2986𝐸+07
21	2.41	d-catechin	C15H14O6	3.7822𝐸+09	4.2278𝐸+09	2.6339𝐸+09	2.5982𝐸+09
22	2.63	Methyl gallate	C8H8O5	2.3823𝐸+10	2.4116𝐸+10	2.3388𝐸+10	—
23	2.63	Salicylic acid	C7H6O3	2.3823𝐸+10	2.4116𝐸+10	2.3388𝐸+10	1.7399𝐸+10
24	2.72	Albiflorin R1	C23H28O11	5.2469𝐸+08	5.6725𝐸+08	5.6329𝐸+08	4.5647𝐸+08
25	3.00	Kaempferol-3,7-di-O-glucoside	C27H30O16	3.8065𝐸+07	2.1896𝐸+07	3.5719𝐸+07	1.5513𝐸+07
26	3.00	Paeonoside	C27H30O16	3.8065𝐸+07	2.1896𝐸+07	3.5719𝐸+07	1.5513𝐸+07
27	3.46	Galloylpaeoniflorin	C30H32O15	1.3912𝐸+08	1.5200𝐸+08	1.1501𝐸+08	1.0863𝐸+08
28	3.47	Paeonolide	C20H28O12	1.0622𝐸+07	1.1936𝐸+07	9.1812𝐸+06	—
29	3.58	6-O-glucopyranosyl-lactinolide	C16H26O9	2.5249𝐸+08	2.3834𝐸+08	2.2675𝐸+08	2.1241𝐸+08
30	3.68	Oxypaeoniflorin	C23H28O12	1.5407𝐸+08	—	1.4345𝐸+08	1.3307𝐸+08
31	3.76	6-O-glucopyranosyl-lactinolide	C16H26O9	3.2664𝐸+08	—	3.0588𝐸+08	3.1627𝐸+08
32	3.88	Paeonilactone B	C10H12O4	9.0325𝐸+07	9.3539𝐸+07	5.1257𝐸+07	8.9597𝐸+07
33	3.93	Isomaltopaeoniflorin	C29H38O16	1.1545𝐸+10	1.1941𝐸+10	1.2282𝐸+10	9.4600𝐸+09
34	4.07	Albiflorin	C23H28O11	2.9587𝐸+10	2.9296𝐸+10	2.8430𝐸+10	2.8684𝐸+10
35	4.32	Glucopyranosylalbiorin	C29H38O16	2.2813𝐸+09	2.4109𝐸+08	2.0383𝐸+08	1.6844𝐸+08
36	4.34	Galloylpaeoniflorin sulfonate	C30H32O17S	7.6943𝐸+08	5.6793𝐸+08	1.5501𝐸+08	1.4886𝐸+09
37	4.34	Galloylpaeoniflorin isomer	C30H32O15	6.7592𝐸+08	7.4322𝐸+08	6.0470𝐸+08	5.4051𝐸+08
38	4.38	1,2,3,6-tetra-O-galloylglucose	C34H28O22	4.6602𝐸+08	3.4977𝐸+08	4.0697𝐸+08	3.6901𝐸+08
39	4.38	Tetragalloyl glucose A	C34H28O22	4.6602𝐸+08	3.4977𝐸+08	4.0697𝐸+08	3.6901𝐸+08
40	4.56	Mudanpioside F	C16H24O8	8.4156𝐸+07	8.2734𝐸+07	7.2666𝐸+07	7.9227𝐸+07
41	4.60	Oxypaeoniflorin isomer	C23H28O12	9.6610𝐸+08	9.8706𝐸+08	9.2464𝐸+08	8.7359𝐸+08
42	4.65	Gallotannin	C27H24O18	6.7737𝐸+07	—	—	—
43	4.77	Paeoniflorin	C23H28O11	5.9556𝐸+10	6.1356𝐸+10	5.9929𝐸+10	5.8832𝐸+10
44	4.89	Paeoniflorin sulfonate II	C23H28O13S	1.1095𝐸+08	1.4567𝐸+08	5.5052𝐸+07	2.7813𝐸+08
45	4.98	Isogalloylpaeoniflorin sulfonate	C30H32O17S	3.6742𝐸+07	—	—	—
46	5.05	Ethyl gallate	C9H10O5	6.0669𝐸+07	5.4850𝐸+07	1.6681𝐸+07	2.6790𝐸+07
47	5.05	Methyl salicylate	C8H8O3	6.0669𝐸+07	5.4850𝐸+07	1.6681𝐸+07	2.6790𝐸+07
48	5.15	Benzoic acid	C7H6O2	4.0163𝐸+07	4.5493𝐸+07	2.9695𝐸+07	2.9727𝐸+07
49	5.25	Paeonol	C9H10O3	6.8567𝐸+07	7.4129𝐸+07	9.9992𝐸+07	6.5619𝐸+07
50	5.25	4-hydroxy-3-methoxy acetophenone	C9H10O3	6.8567𝐸+07	7.4129𝐸+07	9.9992𝐸+07	6.5619𝐸+07
51	5.31	ortho-oxypaeoniflorin	C23H28O12	1.9080𝐸+09	1.9263𝐸+09	1.8723𝐸+09	1.6842𝐸+09
52	5.63	Ethyl gallate	C9H10O5	1.4627𝐸+08	1.2812𝐸+08	1.0365𝐸+08	8.8155𝐸+07
53	5.63	Methyl salicylate	C8H8O3	1.4627𝐸+08	1.2812𝐸+08	1.0365𝐸+08	8.8155𝐸+07
54	5.66	Kaempferol-3-O-glucoside	C21H20O11	1.6012𝐸+07	1.7385𝐸+07	—	—
55	5.66	Astragalin	C21H20O11	1.6012𝐸+07	1.7385𝐸+07	—	—
56	6.01	Eugeniin	C41H30O26	2.7483𝐸+08	3.0279𝐸+08	2.8080𝐸+08	3.0479𝐸+08
57	6.01	Dihydroxymethyl benzoyl tetragalloyl glucose	C41H30O26	2.7483𝐸+08	3.0279𝐸+08	2.8080𝐸+08	3.0479𝐸+08
58	6.03	1,2,3,6-tetra-O-galloylglucose isomer A	C34H28O22	1.3555𝐸+09	—	1.1980𝐸+09	1.1039𝐸+09
59	6.03	Tetragalloyl glucose B	C34H28O22	1.3555𝐸+09	—	—	—
60	6.08	Astragalin	C21H20O11	1.5009𝐸+07	1.8552𝐸+07	1.5922𝐸+07	1.4002𝐸+07
61	6.09	Isomaltopaeoniflorin isomer	C29H38O16	7.5172𝐸+07	—	—	—
62	6.47	1,2,3,6-tetra-O-galloylglucose isomer B	C34H28O22	1.5882𝐸+09	—	—	1.2570𝐸+09
63	6.47	Tetragalloyl glucose C	C34H28O22	1.5882𝐸+09	—	—	1.2570𝐸+09
64	6.85	3,6-di-O-galloyl paeoniorin	C37H36O19	7.6512𝐸+07	—	—	—
65	6.96	1,2,3,6-tetra-O-galloylglucose	C34H28O22	4.4729𝐸+08	4.5825𝐸+08	4.0642𝐸+08	4.2393𝐸+08
66	6.96	Tetragalloyl glucose D	C34H28O22	4.4729𝐸+08	4.5825𝐸+08	4.0642𝐸+08	4.2393𝐸+08
67	7.35	Galloylpaeoniflorin isomer I	C30H32O15	1.2156𝐸+10	1.2451𝐸+10	1.1484𝐸+10	1.0962𝐸+10
68	7.60	1-O-glucopyranosyl-8-O-benzoyl paeonisuffrone	C23H28O10	4.3983𝐸+07	4.5347𝐸+07	4.4927𝐸+07	3.9869𝐸+07
69	7.71	Glucopyranosylalbiorin isomer I	C29H38O16	7.2982𝐸+07	7.9341𝐸+07	—	1.8872𝐸+07
70	8.18	1-O-glucopyranosyl-8-O-benzoyl paeonisuffrone	C23H28O10	7.4648𝐸+07	8.3204𝐸+07	6.5957𝐸+07	5.9832𝐸+07
71	8.31	Ortho-oxypaeoniflorin	C23H28O12	2.4469𝐸+07	2.4504𝐸+07	2.3932𝐸+07	2.2796𝐸+07
72	8.45	1,2,3,4,6-Penta-O-galloyl–D-glucopyranose	C41H32O26	1.1843𝐸+10	1.0905𝐸+10	1.0518𝐸+10	1.0489𝐸+10
73	8.45	Pentagalloyl glucose	C41H32O26	1.1843𝐸+10	1.0905𝐸+10	1.0518𝐸+10	1.0489𝐸+10
74	8.64	Lactiflorin	C23H26O10	1.0818𝐸+08	1.8628𝐸+08	1.3689𝐸+08	—
75	8.80	Galloylalbiroin	C30H32O15	3.2696𝐸+09	—	—	—
76	9.17	Astragalin	C21H20O11	1.0717𝐸+07	1.3960𝐸+07	1.2843𝐸+07	1.0582𝐸+07
77	9.25	Lactinolide	C10H16O4	2.7251𝐸+07	2.6105𝐸+07	2.1735𝐸+07	3.2770𝐸+07
78	9.29	Galloylpaeoniflorin isomer II	C30H32O15	2.8831𝐸+09	—	2.6829𝐸+09	2.2850𝐸+09
79	9.68	Glucopyranosylalbiorin isomer II	C29H38O16	2.4321𝐸+07	2.6804𝐸+07	2.2576𝐸+07	2.4950𝐸+07
80	9.84	Hexagalloyl glucose	C48H36O30	4.9153𝐸+07	—	6.8676𝐸+08	5.7793𝐸+08
81	9.95	Oxybenzoyl-oxypaeoniflorin	C30H32O14	1.4385𝐸+07	1.6654𝐸+07	1.1051𝐸+07	1.1345𝐸+07
82	10.07	1-O-glucopyranosyl-8-O-benzoylpaeonisuffrone	C23H28O10	3.6916𝐸+09	3.5634𝐸+09	3.1333𝐸+09	3.2106𝐸+09
83	10.29	Albiflorin R1 isomer I	C23H28O11	6.3346𝐸+09	6.6205𝐸+09	5.9528𝐸+09	5.8736𝐸+09
84	10.74	Hexagalloyl glucose	C48H36O30	4.9225𝐸+08	2.5582𝐸+08	1.9395𝐸+09	1.5439𝐸+09
85	10.76	Lactiflorin	C23H26O10	1.2785𝐸+09	3.5174𝐸+09	9.9713𝐸+08	3.4524𝐸+09
86	10.84	Benzoylpaeoniflorin Sulfonate	C30H32O14S	9.0616𝐸+08	6.4075𝐸+08	1.5946𝐸+08	2.1931𝐸+09
87	10.88	3,6-di-O-galloyl paeoniorin	C37H36O19	1.6123𝐸+08	—	—	—
88	10.95	Ortho-oxypaeoniflorin isomer	C23H28O12	5.5563𝐸+07	5.8774𝐸+07	5.7147𝐸+07	5.6640𝐸+07
89	11.52	3,6-di-O-galloyl paeoniorin	C37H36O19	3.6509𝐸+08	3.9290𝐸+08	5.2162𝐸+08	5.3781𝐸+08
90	11.72	3,6-di-O-galloyl paeoniorin isomer	C37H36O19	9.7356𝐸+08	—	1.2523𝐸+09	9.5929𝐸+08
91	11.75	Galloylalbiroin isomer I	C30H32O15	2.3457𝐸+08	—	—	—
92	11.84	Oxypaeoniflorin sulfonate isomer	C23H28O14S	2.1063𝐸+07	1.9747𝐸+07	1.3875𝐸+07	1.0840𝐸+07
93	12.15	1-O-glucopyranosyl-8-O-benzoylpaeonisuffrone	C23H28O10	7.2104𝐸+07	7.1468𝐸+07	6.7309𝐸+07	6.5917𝐸+07
94	12.15	Oxybenzoyl-oxypaeoniflorin	C30H32O14	1.9982𝐸+08	—	—	1.6891𝐸+08
95	12.18	Benzoyloxypaeoniflorin	C30H32O13	2.0822𝐸+08	—	2.0163𝐸+08	1.9074𝐸+08
96	13.42	Benzoyloxypaeoniflorin isomer	C30H32O13	8.6458𝐸+07	6.2282𝐸+07	7.6048𝐸+07	7.2791𝐸+07
97	13.44	Oxybenzoyl-oxypaeoniflorin isomer I	C30H32O14	1.4728𝐸+07	1.7389𝐸+07	1.5360𝐸+07	1.6008𝐸+07
98	13.85	Galloylalbiroin isomer II	C30H32O15	9.6403𝐸+07	1.2196𝐸+08	1.0506𝐸+08	1.0272𝐸+08
99	14.05	Oxybenzoyl-oxypaeoniflorin isomer II	C30H32O14	2.5323𝐸+07	2.9603𝐸+07	2.3556𝐸+07	2.8526𝐸+07
100	14.13	Benzoyloxypaeoniflorin	C30H32O13	3.8096𝐸+07	3.8557𝐸+07	3.7499𝐸+07	3.5800𝐸+07
101	15.07	Benzoyloxypaeoniflorin isomer I	C30H32O13	1.9827𝐸+07	2.3616𝐸+07	—	—
102	15.38	Benzoyloxypaeoniflorin isomer II	C30H32O13	1.1841𝐸+07	1.3730𝐸+07	—	—
103	16.01	Oxybenzoyl-paeoniflorin	C30H32O12	1.8152𝐸+07	—	1.8435𝐸+07	—
104	16.95	Isobenzoylpaeoniflorin	C30H32O12	1.2225𝐸+10	1.3228𝐸+10	1.2158𝐸+10	1.2391𝐸+10
105	16.95	Oxybenzoyl-paeoniflorin isomer I	C30H32O12	1.2225𝐸+10	1.3228𝐸+10	1.2158𝐸+10	1.2391𝐸+10
106	17.23	Benzoylpaeoniflorin Sulfonate	C30H32O14S	1.5680𝐸+07	1.2235𝐸+07	5.6573𝐸+06	3.5831𝐸+07
107	17.48	Isobenzoylpaeoniflorin isomer I	C30H32O12	5.4138𝐸+09	5.4432𝐸+09	5.2522𝐸+09	5.3238𝐸+09
108	17.48	Oxybenzoyl-paeoniflorin isomer II	C30H32O12	5.4138𝐸+09	5.4432𝐸+09	5.2522𝐸+09	5.3238𝐸+09
109	17.86	Benzoyloxypaeoniflorin	C30H32O13	3.4347𝐸+07	3.4852𝐸+07	3.5980𝐸+07	3.8814𝐸+07
110	18.55	Benzoyloxypaeoniflorin isomer	C30H32O13	1.5397𝐸+07	1.7656𝐸+07	1.7246𝐸+07	1.8012𝐸+07
111	18.69	Albiflorin R1 isomer II	C23H28O11	2.0046𝐸+07	1.9851𝐸+07	2.3462𝐸+07	—
112	19.30	Albiflorin R1 isomer III	C23H28O11	2.9827𝐸+06	—	—	5.6105𝐸+06
113	21.79	Palbinone	C22H30O4	8.9687𝐸+07	1.3174𝐸+08	1.2834𝐸+08	5.7610𝐸+07
114	21.93	Isobenzoylpaeoniflorin isomer II	C30H32O12	4.5356𝐸+08	4.2874𝐸+07	3.4016𝐸+08	2.7347𝐸+08
115	21.93	Oxybenzoyl-paeoniflorin isomer III	C30H32O12	4.5356𝐸+08	4.2874𝐸+07	3.4016𝐸+08	2.7347𝐸+08
116	22.15	Paeonilactinone	C10H16O2	7.0423𝐸+06	3.7108𝐸+06	8.0036𝐸+06	6.6886𝐸+06
117	36.46	Hederagenin	C30H48O4	7.6725𝐸+07	8.1456𝐸+07	9.7498𝐸+07	4.7332𝐸+07
118	37.31	23-hydroxybetulinic acid	C30H48O4	3.9836𝐸+07	4.0995𝐸+07	3.9906𝐸+07	2.2611𝐸+07
119	38.14	Astrantiagenin D	C30H46O4	7.8714𝐸+06	7.9560𝐸+06	1.1904𝐸+07	3.8958𝐸+06
120	43.00	Astrantiagenin D isomer	C30H46O4	4.0450𝐸+06	—	3.1585𝐸+06	—
121	45.65	Oleanolic acid	C30H48O3	1.1266𝐸+08	9.4258𝐸+07	7.6434𝐸+07	4.3295𝐸+07
122	46.10	Betulinic acid	C30H48O3	6.2494𝐸+06	2.3289𝐸+07	4.0543𝐸+07	2.3912𝐸+07
123	52.48	Daucosterol	C35H60O6	1.4060𝐸+07	1.9624𝐸+07	8.5440𝐸+06	6.3156𝐸+06