Simultaneous Determination of 78 Compounds of Rhodiola rosea Extract by Supercritical CO₂-Extraction and HPLC-ESI-MS/MS Spectrometry

Table 2

Polyphenols and other substances identified from the SC-CO₂ extracts of Rh. rosea.

No.	Compound group	Identification	Formula	Calculated mass	Observed mass [M-H]^−	Observed mass [M+H]^+	Observed mass [M+Na]^+	MS/MS stage 1 fragmentation	MS/MS stage 2 fragmentation	References
Polyphenols
1	Flavonol	Acacetin [linarigenin; buddleoflavonol]	C16H12O5	284.2635	—	285	—	240	212; 183; 165	Mentha [51]; Ocimum [41]
2	Flavonol	Kaempferol	C15H10O6	286.2363	—	287.11	—	269; 189; 133	213; 119	Rhodiola sachalinensis [52, 53]; Rhodiola crenulata [35, 54]; Rhodiola sacra [55]; Impatiens glandulifera Royle [56]
3	Flavonol	Quercetin	C15H10O7	302.2357	—	303.09	—	123; 147; 201; 233; 256	135; 175; 201	Rhodiola rosea [57]; Rhodiola dumulosa [58]; Rhodiola crenulata [35, 59]; Impatiens glandulifera Royle [56]; Eucalyptus [42]; Triticum [43]
4	Flavonol	Herbacetin (3, 5, 7, 8-tetrahydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one)	C15H10O7	302.2357	—	303.08	—	285	212; 268	Rhodiola rosea [3, 60–62]; Rhodiola crenulata [35]; Ocimum [41]
5	Flavonol	Dihydroquercetin (taxifolin; taxifoliol)	C15H12O7	304.2516	—	305.1	—	287; 269; 249; 231; 217; 147	269; 227; 213; 173; 161	Larix dahurica [63]; Eucalyptus [42]; Vitis vinifera [37]
6	Flavonol	Herbacetin 8-methyl ether	C16H12O7	316.2623	—	317.06	—	298; 183; 112	279; 228; 129	Rhodiola crenulata [35]; Rhodiola dumulosa [64]
7	Flavonol	Gossypetin (articulatidin; equisporol; 8-methoxy-hydroxyquercetin)	C15H10O8	318.2351	—	319.03	—	300.97	228; 166; 110	Rhodiola rosea [3, 62]
8	Flavonol	Mearnsetin	C16H12O8	332.2617	—	333.1	—	317; 292; 195	221; 183	Eucalyptus [42]
9	Flavonol	Rhodalin (herbacetin-8-O-beta-D-xylopyranoside)	C20H18O11	434.3503	—	434.96	—	389.90; 266.93	308; 345; 267; 167	Rhodiola rosea [17]
10	Flavonol	Taxifolin-O-pentoside	C20H20O11	436.371	—	436.99	—	391; 285; 177	352; 269; 173	Vitis vinifera [37]
11	Flavonol	Quercitrin (quercetin 3-L-rhamnoside; quercetrin)	C21H20O11	448.3769	—	448.90	—	302.95	169; 303	Lotus japonicus [65]; Rhodiola rosea [62]; Rhodiola crenulata [35, 59]
12	Flavonol	Rhodiolatuntoside	C21H20O11	448.3769	—	450.92	—	332.90	200.89; 154.87	Rhodiola sachalinensis [66]; Rhodiola crenulata [67]
13	Flavonol	Rhodiolinin (rhodiolin)	C25H20O10	480.4203	—	480.95	—	401; 313; 233; 173	357; 313; 269; 233; 145	Rhodiola rosea [2, 16]; Rhodiola sachalinensis [52, 53, 68]; Rhodiola crenulata [69]
14	Flavonole glycoside	Kaempferol-3-xylosyl-glycoside	C26H28O15	580.4915	—	581.09	—	331; 509; 469; 375; 243	330.89; 287.99; 141.74	Rhodiola rosea [61]
15	Flavonole glycoside	Rhodiosin	C27H30O16	610.5175	—	610.82	—	303; 449	169	Rhodiola rosea [2, 16, 70, 71]; Rhodiola sachalinensis [52, 68]; Rhodiola crenulata [69]
16	Flavonole glycoside	Rhodiolgidin	C27H30O17	626.5179	—	627.30	—	344.78	344.7	Rhodiola rosea [3, 17]; Rhodiola crenulata [35]
17	Flavan-3-ol	Catechin	C15H14O6	290.2681	—	291.97	—	250	227	Rhodiola rosea [50]; Rhodiola crenulata [35]; strawberry, cherimoya [36]; pear [45]
18	Flavan-3-ol	Epicatechin ((2R,3R)-2-(3,4-dihydroxyphenyl)-3,5,7-chromanetriol)	C15H14O6	290.2681	—	291.1	—	261; 273; 217; 173; 163	243; 191; 173; 143	Rhodiola rosea [50]; Rhodiola crenulata [35]; Rhodiola kirilowii [72]
19	Flavan-3-ol	Gallocatechin ((+)-gallocatechin)	C15H14O7	306.27	305.06	—	—	179; 168; 261	124	Red wine [73]; Licania ridigna [74]
20	Flavan-3-ol	(-)-Epicatechin gallate	C22H18O10	442.3723	—	443.01	—	363.12	319.16	Rhodiola rosea [39]; Rhodiola crenulata [35, 75]; Rhodiola kirilowii [50, 76]
21	Flavanone	Eriodictyol-7-O-glucoside (pyracanthoside; miscanthoside)	C21H22O11	450.3928	—	451.00	—	333; 433; 155	288; 201	Impatiens glandulifera Royle [56]
22	Flavone	Luteolin	C15H10O6	286.2363	285.02	—	—	241; 168; 124	124.02	Rhodiola crenulata [35, 54]; Rhodiola kirilowii [72]; Rhodiola sachalinensis [53, 77]
23	Flavone	Tricin	C17H14O7	330.2889	329.18	—	—	299; 311; 229; 171	211.04; 125.14	Triticum aestivum L. [77, 78]; Rhodiola rosea [61, 79]; Rhodiola sacra [55]; Rhodiola sachalinensis [53]; Rhodiola crenulata [59]
24	Flavone	Luteolin-7-O-α-L-rhamnoside	C21H20O10	432.3775	430.99	—	—	284.93	283.93	Rhodiola crenulata [35];
25	Flavone	Tricin 7-O-glucoside	C23H24O12	492.4295	—	493.11	—	401; 292; 201	383; 329; 280; 156	Rhodiola rosea [61, 70, 79]; Rhodiola crenulata [59]
26	Flavone	Apigenin-O-hexoside derivative	C26H25O12	529.4695	—	531.08	—	433; 485; 243; 177	399; 310	Strawberry [36]
27	Flavone	Tricetin trimethyl ether, 7-O-hexoside malonylated	C27H28O15	592.5022	591.23	—	—	533; 437; 323	197.01	Triticum aestivum L. [77]
28	Flavone	Tricin, 7-O-glucoronyl-O-hexoside	C29H32O18	668.5536	—	669.13	—	419; 375; 271	375; 243; 171	Triticum aestivum L. [77]
29	Flavone	Tricin trimethyl ether, 7-O-hexosyl-hexoside	C30H36O17	668.5966	—	669.01	—	419; 557; 331; 287	375; 331; 215	Triticum aestivum L. [77]
30	Flavone	Tricin, O-pentoside; O-dihexoside	C35H44O21	800.7113	—	801.24	—	409; 655; 509; 252	—	Triticum aestivum L. [77]
31	Hydroxycinammic acid	Ferulic acid	C10H10O4	194.184	—	195.07	—	176.8	—	Rhodiola crenulata [35]; Triticum [43]
32	Hydroxycinammic acid	Caffeoylmalic acid	C13H12O8	296.2296	—	297.09	—	279; 211; 163	265; 163; 135	Strawberry [36]
33	Cinnamate ester	4-O-p-Coumaroylquinic acid	C16H18O8	338.3098	—	338.94	—	189; 151	—	Pear [45]
34	Cinnamic alcohol glycoside)	Rosin (trans-cinnamyl O-beta-D-glycopyranoside)	C15H20O6	296.3157	—	297.06	—	255; 179; 115	215; 110	Rhodiola rosea [16, 49, 80]; Rhodiola crenulata [35]; Rhodiola sachalinensis [53]
35	Cinnamic alcohol glycoside	Triandrin	C15H20O7	312.3151	—	313.21	—	268.14	240; 211; 193	Rhodiola crenulata [35, 54]; Rhodiola rosea [10, 81]
36	Cinnamic alcohol glycoside	Sachaliside 1	C15H20O7	312.3151	311.13	—	—	309.08; 182.96	247.08; 119.01	Rhodiola rosea [9]
37	Cinnamic alcohol glycoside	p-Hydroxyphenacyl-β-D-glucopyranoside	C14H18O8	314.2879	—	314.97	—	294; 163	—	Rhodiola crenulata [35, 82];
38	Cinnamic alcohol glycoside	(2E)-3-(4-methoxyphenyl)-2-propen-1-yl-beta-D-glycopyranoside	C16H22O7	326.3417	325.09	—	—	182.99	119.09	Rhodiola rosea [9]
39	Cinnamic alcohol glycoside	Coniferin	C16H22O8	342.3411	—	343.01	—	240; 301; 129	240; 183	Rhodiola crenulata [35, 54]
40	Phenylpropanoid (cinnamicacid derivative glycoside)	Chlorogenic acid (3-O-caffeoylquinic acid)	C16H18O9	354.3087	—	355.04	—	335; 285; 203	200.0	Rhodiola rosea [2]; Eucalyptus [42]; Triticum [43];
41	Cinnamic alcohol glycoside	Rosavin (trans-cinnamil O-(6′-O-alpha-L-arabinopyranosyl-beta-D-glycopyranoside)	C20H28O10	428.4303	—	—	451.00	333; 155; 201	200.94	Rhodiola rosea [16, 49, 83]; Rhodiola crenulata [84]; Rhodiola sachalinensis [53]; Rhodiola quadrifida [2, 85]
42	Cinnamic alcohol glycoside	Rosarin (trans-cinnamyl O-(6′-O-alpha-L arabinofuranosyl-beta-D-glycopyranoside)	C20H28O10	428.4303	—	429.01	—	285; 199	384; 328; 230; 159	Rhodiola rosea [9, 16, 49, 83]; Rhodiola sachalinensis [53]
43	Phenylpropanoid (cinnamic acid derivative)	Di-O-caffeoylquinic acid	C25H24O12	516.4509	—	516.86	—	352; 431; 276	200; 135	Pear [45]
44	Gallic acid derivative	6-O-galloyl-salidroside	C21H24O11	452.4087	—	453.09	—	435; 209; 336	226; 336; 417	Rhodiola crenulata [35, 54]; Rhodiola rosea [39]
45	Gallic acid derivative	1,2,6-Tri-O-galloyl-beta-D-glucoside	C27H24O18	636.4687	—	637.28	—	507; 566; 620; 488; 366; 189	—	Rhodiola rosea [39]
46	Anthocyanidin	Pelargonidin-3-glucoside (callistephin)	C21H21ClO10	468.8444	—	469.88	—	357.05	247.00	Triticum [43]
47	Anthocyanidin	Pelargonidin (3-O-(6-O-malonyl-beta-D-glucoside))	C24H23O13	519.4388	—	520.10	—	433; 184	307; 163	Gentiana lutea [86]; wheat [87]
48	Proanthocyanidin	Proanthocyanidin B1 (procyanidin B1; procyanidin dimer B1)	C30H26O12	578.5202	577.21	579.07	—	197; 254; 351; 393; 407; 421	196.94; 133.04; 182.93	Pear [45]; Eucalyptus [42]
49	Anthocyanidin	Cyanidin-3-(3″,6″-dimalonylglucoside)	C27H24O17	620.4773	—	621.17	—	619; 432; 264	601; 518; 419	Wheat [87]
50	Anthocyanidin	Pelargonidin (3-O-(6-O-malonyl-beta-D-glucoside)-5-beta-D-glucoside	C30H33O18	681.5812	—	682.10	—	515.58; 353.14	351; 295; 173	Gentiana lutea [86]
51	Coumarin	Esculetin (cichorigenin; esculetin)	C9H6O4	178.1415	—	179.02	—	147.01	119.03	Ledum palustre [38]; Vitis vinifera [37]
52	Coumarin	Esculin (esculin; esculoside; polichrome)	C15H16O9	340.2821	—	340.91	—	133; 283; 322	175; 133	Dog plasma [38]; rat plasma [88]
53	Coumarin glucoside	Fraxin (Fraxetin-8-O-glucoside)	C16H18O10	370.3081	—	370.97	—	356; 193; 123	207.02	Dog plasma [38]; rat plasma [88]
54	Lignan	Hinokinin	C20H18O6	354.3533	—	355.01	—	337; 283; 203	239; 133	Triticum aestivum L. [89]; Bursera simaruba [90]
55	Lignan	Pinoresinol	C20H22O6	358.3851	—	359.02	—	341; 187	323; 187	Triticum aestivum L. [78]; Eucommia cortex [47]
56	Aryl-beta-glycoside	Arbutin	C12H16O7	272.2512	—	273.17	—	217; 163	161.09	Strawberry, blueberry, pear [91]; pear [45]
Others
57	Natural water-soluble vitamin	L-ascorbic acid	C6H8O6	176.1241	—	176.98	—	145.00	117.03	Strawberry, lemon, papaya [36]
58	Aldaric acid	Glucaric acid (D-glucaric acid)	C6H10O8	210.1388	—	211.01	—	192; 115	129.05	Cherimoya, papaya [36]
59	Monobasic saturated carboxylic acid	Palmitic acid (hexadecanoic acid; palmitate)	C16H32O2	256.4241	—	257.02	—	237; 137	221; 125	Salviae [44]
60	Acyclic alcohol nitrile glycoside	Heterodendrin ((2R)-2-(β-D-glucopyranosyloxy)-3-methylbutanenitrile)	C11H19O6N	261.2717	—	263.96	—	155; 228	—	Rhodiola crenulata [35]
61	Monobasic saturated carboxylic acid	Linolenic acid (alpha-linolenic acid; linolenate)	C18H30O2	278.4296	—	279.1	—	261; 243; 187; 123	173; 131	Salviae [44]; rice [48]
62	Phenylethane glycoside	Picein (ameliaroside; salicinerin; salinigrin; piceoside)	C14H18O7	298.2901	—	299	—	271; 211; 179	254; 225; 197	Rhodiola rose [9]; Rhodiola crenulata [82]
63	Phenylethane glycoside	Salidroside (2-(4-hydroxyphenyl) ethyl β-D-glucopyranoside)	C14H20O7	300.3044	—	301.15	—	240; 201	183; 110	Rhodiola crenulata [35, 54]; Rhodiola rosea [1, 92, 93]; Rhodiola sachalinensis [53]; Rhodiola kirilowii [2]
64	Phenylethane glycoside	Icariside D2	C14H20O7	300.3044	—	301.06	—	240; 201; 135	183; 113	Rhodiola rosea [39]; Rhodiola crenulata [54, 82]; Rhodiola sacra [55];
65	Acyclic alcohol glycoside	Creoside II	C14H26O7	306.352	—	307.99	—	199; 255	—	Rhodiola crenulata [35, 54]
66	Phenylethane glycoside	Viridoside	C15H22O7	314.331	—	315.04	337.11	319.13; 209.08	151; 207; 262; 301	Rhodiola viridula [94]; Rhodiola rosea [83]; Rhodiola crenulata [35]; Rhodiola sachalinensis [53]
67	Acyclic alcohol glycoside	Rosiridin (3,7-dimethylocta-2,6-diene-1,4-diol; 1-O-beta-D-glucopyranoside)	C16H28O7	332.3893	—	333.02	—	247; 175	181.93	Rhodiola crenulata [35]; Rhodiola rosea [2, 17, 49]; Rhodiola sachalinensis [95]
68	Acyclic alcohol glycoside	Rhodioloside A	C16H28O8	348.3887	—	349.02	371.03	271; 281; 305; 331; 257; 231; 219; 167; 141	268; 256; 243; 229; 215; 193; 143	Rhodiola rosea [1, 92]; Rhodiola crenulata [35]
69	Acyclic alcohol glycoside	Rhodioloside D	C16H30O8	350.4046	—	351.06	—	258; 220; 131	257; 141	Rhodiola rosea [1, 83, 92]; Rhodiola crenulata [35]
70	Tetracyclic diterpenoid	Grayanotoxin II	C20H32O5	352.4651	—	353.04	—	335; 282; 203	315; 245; 113	Grayanotoxins [96]
72	Benzidine glycoside	Phenylmethyl (6-O-alpha-L-arabinopyranosyl-beta-D-glycopyranoside)	C18H26O10	402.3930	—	402.86	—	343; 283; 175	283	Rhodiola rosea [83]; Rhodiola sachalinensis [53]
73	Acyclic alcohol glycoside	Rhodiooctanoside	C19H36O10	424.4831	—	424.94	—	290.96	173; 261	Rhodiola crenulata [35, 54]; Rhodiola kirilowii [97]; Rhodiola sacra [98]
74	Phenylethane glycoside	Mongrhoside	C20H30O11	446.4456	—	446.65	—	243; 379; 311	174.84	Rhodiola rosea [83]
75	Acyclic alcohol glycoside	Creoside V	C21H38O10	450.5204	—	473.15	—	471; 254; 401	463.61	Rhodiola crenulata [35];
76	Hydroxy acid	Ursolic acid	C30H48O3	456.7003	—	457.17	—	412; 307	368; 269	Ocimum [41]; pear [45]
77	Acyclic alcohol glycoside	Rhodioloside E	C21H38O11	466.5198	—	467.95	—	399.94; 265; 332	331.88	Rhodiola rosea [1, 92]; Rhodiola crenulata [35, 54]; Rhodiola sachalinensis [13]; Rhodiola sacra [55]
78	Acyclic alcohol glycoside	Rhodioloside B	C22H38O12	494.5299	493.22	—	517.97	447; 220	314.98	Rhodiola rosea [1, 92]; Rhodiola crenulata [35]