Separation and Identification of Terpenoids in Three Pineapple Fibers Using Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

Figures & data

Table 1. Mass spectrometry information of terpenoids.

	Metabolite name	Adduct type	Reference m/z	Formula	Ontology	SMILES	MS1 isotopic spectrum
1	3-oxo-3-[[(2 R,3S,4S,5 R,6S)-3,4,5-trihydroxy-6-(4-hydroxy-5-methyl-2-propan-2-ylphenoxy) oxan-2-yl] methoxy] propanoic acid	[M+H]+	437.1418	C19H26O10	Terpene glycosides	O=C(O)CC(=O)OCC1OC(OC2=CC(=C(O)C=C2C(C)C)C)C(O)C(O)C1O	437.1413:2624 438.14465:626 439.14801:803
2	1,5,9-trihydroxy-5,7,7-trimethyl-4,5a,6,8,8a,9-hexahydro-1 H-azuleno[5,6-c] furan-3-one	[M-H]-	281.0996	C15H22O5	Terpene lactones	O=C1OC(O)C2=C1CC(O)(C)C3CC(C)(C)CC3C2O	281.09943:1940 282.10278:354 283.10614:274
3	methyl (4S,5Z,6S)-5-(2-hydroxyethylidene)-4-[2-[2-(4-hydroxyphenyl) ethoxy]-2-oxoethyl]-6-[(2S,3 R,4S,5S,6 R)-3,4,5-trihydroxy-6-(hydroxymethyl) oxan-2-yl] oxy-4 H-pyran-3-carboxylate	[M-H]-	619.1416	C25H32O13	Terpene glycosides	O=C(OC)C1=COC(OC2OC(CO)C(O)C(O)C2O)C(=CCO)C1CC(=O)OCCC3=CC=C(O)C=C3	619.13599:1022 62.13934:542 621.1427:1028
4	(2Z)-2-[4-[2-[2-(3,4-dihydroxyphenyl) ethoxy]-2-oxoethyl]-5-methoxycarbonyl-2-[(2S,3 R,4S,5S,6 R)-3,4,5-trihydroxy-6-(hydroxymethyl) oxan-2-yl] oxy-4 H-pyran-3-ylidene] acetic acid	[M-H]-	569.1512	C25H30O15	Terpene glycosides	O=C(O)C=C1C(OC=C(C(=O)OC)C1CC(=O)OCCC2=CC=C(O)C(O)=C2)OC3OC(CO)C(O)C(O)C3O	569.15393:1901 57.15728:876 571.16064:468
5	[(1S,3 R,3aS,4S,8aR)-1-acetyloxy-3-hydroxy-6,8a-dimethyl-3-propan-2-yl-1,2,3a,4,5,8-hexahydroazulen-4-yl] 4-hydroxybenzoate	[M-H]-	415.2126	C24H32O6	Sesquiterpenoids	O=C(OC1CC(=CCC2(C)C(OC(=O)C)CC(O)(C(C)C)C12)C)C3=CC=C(O)C=C3	415.21115:10911 416.2145:2961 417.21786:15249
6	3-[4-methyl-1-(2-methylpropanoyl)-3-oxocyclohexyl] butanoic acid	[M-H]-	267.1346	C15H24O4	Menthane monoterpenoids	O=C(O)CC(C)C1(C(=O)C(C)C)CC(=O)C(C)CC1	267.13434:1231 268.13769:68 269.14105:306
7	(2 R,6 R)-6-[(3 R,10S,12S,13 R,17 R)-3-(2-carboxyacetyl) oxy-12-hydroxy-4,4,10,13,14-pentamethyl-2,3,5,6,7,11,12,15,16,17-decahydro-1 H-cyclopenta[a]phenanthren-17-yl]-2-methyl-3-methylideneheptanoic acid	[M-H]-	571.1786	C34H52O7	Triterpenoids	O=C(O)CC(=O)OC1CCC2(C3=C(CCC2C1(C)C)C4(C)CCC(C(C)CCC(=C)C(C(=O)O)C)C4(C)C(O)C3)C	571.18579:1660 572.18914:674 573.1925:337
8	3-(Rha (1–2) Glu (1–2) Glu-28-Glu oleanolic acid (NMR)	[M-H]-	1087.569	C54H88O22	Triterpene saponins	C[C@@H]1O[C@@H](O[C@@H]2[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]2O[C@@H]2[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]2O[C@H]2CC[C@@]3(C)C(CC[C@]4(C)C3CC=C3[C@@H]5CC(C)(C)CC[C@@]5(CC[C@@]43C)C(=O)O[C@@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@H]3O)C2(C)C)[C@H](O)[C@H](O)[C@H]1O	1087.58313:5927 1088.58648:6376 1089.58984:2171
9	Chrysanthellin B	[M-H]-	1205.596	C58H94O26	Triterpene saponins	CC1OC(OC2C(O)COC(OC3C(C)OC(OC4C(O)C(O)COC4OC(=O)C45CCC(C)(C)CC4C4=CCC6C7(C)CCC(OC8OC(CO)C(O)C(O)C8O)C(C)(CO)C7CCC6(C)C4(C)CC5O)C(O)C3O)C2O)C(O)C(O)C1O	1205.61609:1790 1206.61944:1820 1207.6228:960
10	[(2S,3 R,4S,5S,6 R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] (4aS,6aS,6bR,9 R,10 R,11S,12aR)-11-hydroxy-9-(hydroxymethyl)-2,2,6a,6b,9,12a-hexamethyl-10-[(2S,3 R,4S,5 R)-3,4,5-trihydroxyoxan-2-yl]oxy-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carboxylate	[M+H]+	805.4634	C41H66O14	Triterpene saponins	O=C(OC1OC(CO)C(O)C(O)C1O)C23CCC(C)(C)CC3C4=CCC5C6(C)CC(O)C(OC7OCC(O)C(O)C7O)C(C)(CO)C6CCC5(C)C4(C)CC2	805.46338:1094 806.46673:770 807.47009:280
11	Ganoderic acid LM2	[M+H]+	515.3	C30H42O7	Triterpenoids	O=C(O)C(=CC(O)CC(C)C1CC(=O)C2(C3=C(C(=O)CC12C)C4(C)CCC(=O)C(C)(C)C4CC3O)C)C	515.29889:1986 516.30224:513 517.3056:172
12	Ginsenoside Rg6	[M-H]-	811.4849	C42H70O12	Triterpenoids	CC1OC(OC2C(O)C(O)C(CO)OC2OC2CC3(C)C(CC(O)C4C(CCC34C)C(=C)CCC=C(C)C)C3(C)CCC(O)C(C)(C)C23)C(O)C(O)C1O	811.48322:49942 812.48657:28250 813.48993:8404
13	[(2E,6Z,10Z)-7,11-bis(acetyloxymethyl)-3,15-dimethylhexadeca-2,6,10,14-tetraenyl] acetate	[M-H]-	447.2752	C26H40O6	Acyclic diterpenoids	O=C(OCC=C(C)CCC=C(COC(=O)C)CCC=C(COC(=O)C)CCC=C(C)C)C	447.27829:1859 448.28164:559 449.285:13
14	[(1S,2 R,4aR,8aR)-1-acetyloxy-1,4a-dimethyl-6-oxo-7-propan-2-ylidene-2,3,4,5,8,8a-hexahydronaphthalen-2-yl] 3-acetyloxy-2-hydroxy-2-methylbutanoate	[M-H]-	451.2337	C24H36O8	Sesquiterpenoids	O=C(OC(C)C(O)(C(=O)OC1CCC2(C)CC(=O)C(=C(C)C)CC2C1(OC(=O)C)C)C)C	451.23962:2142 452.24297:510 453.24633:85
15	Saikosaponin B3	[M+H]+	835.48	C43H72O14	Triterpene saponins	OCC1OC(OC2C(O)C(OC(C)C2O)OC3CCC4(C)C(CCC5(C)C4C(OC)C=C6C7CC(C)(C)CCC7(CO)C(O)CC65C)C3(C)CO)C(O)C(O)C1O	835.46564:4178 836.46899:2505 837.47235:747
16	Ginsenoside Rg2	[M-H]-	783.49	C42H72O13	Triterpene saponins	CC1OC(OC2C(O)C(O)C(CO)OC2OC2CC3(C)C(CC(O)C4C(CCC34C)C(C)(O)CCC=C(C)C)C3(C)CCC(O)C(C)(C)C23)C(O)C(O)C1O	783.47595:19293 784.4793:6064 785.48266:959
17	(3S,4S,6aR,6bS,8 R,8aR,12aS,14bR)-8-hydroxy-4,6a,6b,11,11,14b-hexamethyl-8a-[(2S,3 R,4S,5S,6 R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxycarbonyl-3-[(2S,3 R,4S,5 R)-3,4,5-trihydroxyoxan-2-yl]oxy-1,2,3,4a,5,6,7,8,9,10,12,12a,14,14a-tetradecahydropicene-4-carboxylic acid	[M-2 H]2-	795.4626	C41H64O15	Triterpene saponins	O=C(O)C1(C)C(OC2OCC(O)C(O)C2O)CCC3(C)C1CCC4(C)C3CC=C5C6CC(C)(C)CCC6(C(=O)OC7OC(CO)C(O)C(O)C7O)C(O)CC54C	795.4707:1851 796.47405:8590 797.47741:6570
18	Echinocystic acid-3-O-glucoside	[M-H]-	633.4008	C36H58O9	Triterpene saponins	CC1(C)CCC2(C(O)CC3(C)C(=CCC4C5(C)CCC(OC6OC(CO)C(O)C(O)C6O)C(C)(C)C5CCC34C)C2C1)C(O)=O	633.39001:4465 634.39336:2723 635.39672:1875
19	Saikosaponin a	[M-H]-	825.4642	C42H68O13	Triterpene saponins	CC1OC(OC2CCC3(C)C(CCC4(C)C3C=CC35OCC6(CCC(C)(C)CC36)C(O)CC45C)C2(C)CO)C(O)C(OC2OC(CO)C(O)C(O)C2O)C1O	825.46625:1761 826.4696:1071 827.47296:582
20	3-(Glucosyl (1–2) glucuronyl)-22-DDMP Soyasapogenol B (NMR)	[M-H]-	921.4854	C48H74O17	Triterpene saponins	CC1=C(O)C(=O)C[C@@H](O[C@@H]2CC(C)(C)C[C@H]3C4=CCC5[C@@]6(C)CC[C@H](O[C@@H]7O[C@@H]([C@@H](O)[C@H](O)[C@H]7O[C@@H]7O[C@H](CO)[C@@H](O)[C@H](O)[C@H]7O)C(O)=O)[C@](C)(CO)C6CC[C@@]5(C)[C@]4(C)CC[C@@]23C)O1	921.48346:2036 922.48681:1990 923.49017:874
21	myrcene	[M+H]+	159.12	C10H16	Acyclic monoterpenoids	C=CC(=C)CCC=C(C)C	159.12247:1839 16.12582:362 161.12918:1943
22	2-Hydroxy-5 (6) Epoxy-Tetrahydrocaryophyllene	[M-H]-	237.0847	C15H26O2	Sesquiterpenoids	OC1(C)CCC2OC2(C)CCC3C1CC3(C)C	237.08249:1460 238.08584:348 239.0892:117
23	7-ethenyl-1,4a,7-trimethyl-3,4,6,8,8a,9,10,10a-octahydro-2 H-phenanthrene-1-carboxylic acid	[M-H]-	301.2173	C20H30O2	Diterpenoids	O=C(O)C1(C)CCCC2(C3=CCC(C=C)(C)CC3CCC12)C	301.21164:3963 302.21499:986 303.21835:203
24	(1 R,9S,10S)-3,4-dihydroxy-11,11-dimethyl-5-(propan-2-yl)-16-oxatetracyclo [7.5.2.00,] hexadeca-2(7),3,5-triene-8,15-dione	[M-H]-	343.2279	C20H24O5	Diterpene lactones	O=C1OC2C(=O)C = 3C=C(C(O)=C(O)C3C14CCCC(C)(C)C24)C(C)C	343.22836:1321 344.23171:193 345.23507:989
25	Raddeanin A	[M+Na]+	919.5	C47H76O16	Triterpenoids	O=C(O)C12CCC(C)(C)CC2C3=CCC4C5(C)CCC(OC6OCC(O)C(O)C6OC7OC(CO)C(O)C(O)C7OC8OC(C)C(O)C(O)C8O)C(C)(C)C5CCC4(C)C3(C)CC1	919.49744:1338 92.50079:855 921.50415:370
26	Ginsenoside Rg5	[M-H]-	765.4794	C42H70O12	Triterpene saponins	CC(C)=CCC=C(C)C1CCC2(C)C1C(O)CC1C3(C)CCC(OC4OC(CO)C(O)C(O)C4OC4OC(CO)C(O)C(O)C4O)C(C)(C)C3CCC21C	765.47797:1060 766.48132:988 767.48468:286
27	dehydroabietic acid	[M-H]-	299.2016	C20H28O2	Diterpenoids	O=C(O)C1(C)CCCC2(C3=CC=C(C=C3CCC12)C(C)C)C	299.19531:1416 3.19866:214 301.20202:259
28	9-hydroxy-9-[[(E)-2-(hydroxymethyl)-3-[3-(hydroxymethyl)-6-propan-2-ylcyclohex-2-en-1-yl] prop-2-enoyl] oxymethyl]-1-oxo-6-propan-2-yl-3,5a,6,7,8,9a-hexahydro-2-benzoxepine-4-carboxylic acid	[M-H]-	533.2145	C29H42O9	Terpene lactones	O=C(O)C1=CC2C(C(=O)OC1)C(O)(COC(=O)C(=CC3C=C(CO)CCC3C(C)C)CO)CCC2C(C)C	533.2149:1338 534.21825:371 535.22161:154
29	(2 R,3 R,4S,5S,6 R)-2-[(E)-5-[(1 R,4aS,5S,6 R,8aS)-6-hydroxy-5,8a-dimethyl-2-methylidene-5-[[(2 R,3 R,4S,5S,6 R)-3,4,5-trihydroxy-6-(hydroxymethyl) oxan-2-yl] oxymethyl]-3,4,4a,6,7,8-hexahydro-1 H-naphthalen-1-yl]-3-methylpent-2-enoxy]-6-(hydroxymethyl) oxane-3,4,5-triol	[M-H]-	645.4141	C32H54O13	Diterpene glycosides	OCC1OC(OCC=C(C)CCC2C(=C)CCC3C(C)(COC4OC(CO)C(O)C(O)C4O)C(O)CCC23C)C(O)C(O)C1O	645.42102:1031 646.42437:590 647.42773:197
30	[(2 R,3S,4S,5 R,6S)-6-[(2S,3 R,4S,5 R,6 R)-6-[[(1S,3 R,4S,4aR,8aR)-4-[(3S)-3-[(2S,3 R,4 R,5 R,6 R)-3,4-dihydroxy-6-methyl-5-[(2S,3 R,4 R,5 R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-3-methylpent-4-enyl]-3,4,8,8a-tetramethyl-1,2,3,4a,5,6-hexahydronaphthalen-1-yl]oxy]-4,5-dihydroxy-2-methyloxan-3-yl]oxy-3,4,5-trihydroxyoxan-2-yl]methyl acetate	[M-H]-	947.4857	C46H76O20	Diterpene glycosides	O=C(OCC1OC(OC2C(O)C(O)C(OC2C)OC3CC(C)C(C)(CCC(OC4OC(C)C(OC5OC(C)C(O)C(O)C5O)C(O)C4O)(C=C)C)C6CCC=C(C)C36C)C(O)C(O)C1O)C	947.49744:1295 948.50079:773 949.50415:360
31	alpha-Hederin	[M-H]-	749.4481	C41H66O12	Triterpenoids	CC1OC(OC2C(O)C(O)COC2OC2CCC3(C)C(CCC4(C)C3CC=C3C5CC(C)(C)CCC5(CCC43C)C(O)=O)C2(C)CO)C(O)C(O)C1O	749.44275:1393 75.4461:940 751.44946:309
32	14-(hydroxymethyl)-5,9-dimethyltetracyclo [11.2.1.00,] hexadecan-5-ol	[M-H]-	291.2116	C19H32O2	Kaurane diterpenoids	OCC1CC23CCC4C(O)(C)CCCC4(C)C3CCC1C2	291.20853:1401 292.21188:268 293.21524:220
33	(1S,9S, E)-4,11,11-trimethyl-8-methylenebicyclo [7.2.0] undec-4-ene	[M+H]+	227.18	C15H24	Sesquiterpenoids	C=C1CCC=C(C)CCC2C1CC2(C)C	227.18091:2073 228.18426:398 229.18762:88
34	(2alpha,3beta)-2,3-dihydroxyolean-12-en-28-oic acid	[M+H]+	495.35	C30H48O4	Triterpenoids	O=C(O)C12CCC(C)(C)CC2C3=CCC4C5(C)CC(O)C(O)C(C)(C)C5CCC4(C)C3(C)CC1	495.35803:1922 496.36138:874 497.36474:2542
35	3-[(Z)-5-[6-hydroxy-5,5,8a-trimethyl-2-methylidene-3-[3,4,5-trihydroxy-6-(hydroxymethyl) oxan-2-yl] oxy-3,4,4a,6,7,8-hexahydro-1 H-naphthalen-1-yl]-3-methylpent-2-enoxy]-3-oxopropanoic acid	[M+H]+	593.2932	C29H46O11	Diterpene glycosides	O=C(O)CC(=O)OCC=C(C)CCC1C(=C)C(OC2OC(CO)C(O)C(O)C2O)CC3C(C)(C)C(O)CCC13C	593.29437:6953 594.29772:4832 595.30108:1044

Figure 1. UHPLC-MS/MS mass spectrum of pineapple fiber. A represented the positive ion chromatogram, B represented the negative ion chromatogram, and C represented the peak value of total terpene content.

Figure 2. Proportion and molecular formula of different terpenoids in different pineapple fibers.

Figure 3. S-plot analysis of terpenoids in pineapple fibers. A represented VIP values of terpenoids in three pineapple fibers, and B, C and D represented S-plot diagrams of PLF-PSF, PLF-PRF and PSF-PRF, respectively.

Figure 4. Thermogram and correlation analysis of terpenoids in three kinds of pineapple fibers. A represented thermographic analysis of terpenoids. B represented the correlation analysis of terpenoids. C represented the structural formula of differential terpenoids.