Table 2.

Qualitative characterization of phenolic compounds in black pepper, black cumin and black cardamom by LC-ESI-QTOF/MS in positive and negative ionization modes

Peak no.	Proposed compound	Molecular formula	RT (min)	Ionization mode	Molecular weight	Theoretical (m/z)	Observed (m/z)	Mass error (ppm)	Sample name
Phenolic acids
Hydroxycinnamic acids
1	Cinnamic acid	C9H8O2	9.169	[M + H]+	148.0524	149.0597	149.0590	− 4.70	BCM2
2	3-Sinapoylquinic acid	C18H22O10	9.655	[M − H]−	398.1213	397.1140	397.1144	0.50	BP2
3	Caffeic acid 3-O-glucuronide	C15H16O10	11.306	[M − H]−	356.0743	355.0670	355.0698	7.89	BCM2
4	1,2-Disinapoylgentiobiose	C34H42O19	13.655	[M + H]+	754.2320	755.2393	755.2400	0.93	BP2
5	Ferulic acid 4-O-glucoside	C16H20O9	18.048	[M − H]−	356.1107	355.1034	355.1062	7.89	BCM2
6	Isoferulic acid	C10H10O4	18.197	[M + H]+	194.0579	195.0652	195.0645	− 3.59	BCM2
7	Caffeic acid 3-sulfate	C9H8O7S	19.522	[M − H]−	259.9991	258.9918	258.9938	7.72	BCM2
8	Chlorogenic acid	C16H18O9	19.884	[M + H]+	354.0951	355.1024	355.1010	− 3.94	*BP2, BCM2
9	3-O-Methylrosmarinic acid	C19H18O8	20.069	[M + H]+	374.1002	375.1075	375.1070	− 1.33	BCM1
10	Feruloyl tartaric acid	C14H14O9	22.145	[M − H]−	326.0638	325.0565	325.0583	5.54	BCD1
11	p-Coumaroyl glycolic acid	C11H10O5	25.038	[M + H]+	222.0528	223.0601	223.0596	− 2.24	BCM2
12	p-Coumaroyl malic acid	C13H12O7	25.375	[M − H]−	280.0583	279.0510	279.0511	0.36	BP1
13	3,4-O-Dimethylgallic acid	C9H10O5	25.375	[M − H]−	198.0528	197.0455	197.0474	9.64	BP1
14	Avenanthramide 2f	C17H15NO6	33.409	[M − H]−	329.0899	328.0826	328.0816	− 3.05	BP2
15	Caffeic acid	C9H8O4	19.146	*[M − H]−/[M + H]+	180.0423	179.0350	179.0349	− 0.56	BP2, *BCD2
16	m-Coumaric acid	C9H8O3	34.353	[M − H]−	164.0473	163.0400	163.0416	9.81	BCD1
17	p-Coumaroyl tyrosine	C18H17NO5	35.074	[M + H]+	327.1107	328.1180	328.1170	− 3.05	BP1
18	Sinapic acid	C11H12O5	35.988	[M − H]−	224.0685	223.0612	223.0621	4.03	BCM2
19	p-Coumaroyl tartaric acid	C13H12O8	49.461	[M − H]−	296.0532	295.0459	295.0483	8.13	*BP1, BCM1
20	p-Coumaric acid ethyl ester	C11H12O3	81.116	[M − H]−	192.0786	191.0713	191.0715	1.05	BCD1
21	Rosmarinic acid	C18H16O8	81.838	[M + H]+	360.0845	361.0918	361.0920	0.55	BCD2
Hydroxybenzoic acids
22	Vanillicacid 4-sulfate	C8H8O7S	8.921	[M − H]−	247.9991	246.9918	246.9937	7.69	BCM1
23	Protocatechuic acid 4-O-glucoside	C13H16O9	9.092	[M − H]−	316.0794	315.0721	315.0724	0.95	BP1
24	Protocatechuic acid	C7H6O4	12.289	[M − H]−	154.0266	153.0193	153.0205	7.84	*BP2, BCM2
25	4-O-Methylgallic acid	C8H8O5	14.359	*[M − H]−/[M + H]+	184.0372	183.0299	183.0301	1.09	*BP2, BCM2
26	Hippuricacid	C9H9NO3	14.569	[M + H]+	179.0582	180.0655	180.0643	− 6.66	BCM2
27	p-Hydroxybenzoic acid	C7H6O3	19.903	[M − H]−	138.0317	137.0244	137.0257	9.49	BP2, *BCM2
28	Paeoniflorin	C23H28O11	66.567	[M − H]−	480.1632	479.1559	479.1570	2.30	BCM2
Hydroxyphenylacetic acids
29	3,4-Dihydroxyphenylacetic acid	C8H8O4	23.735	*[M − H]−/[M + H]+	168.0423	167.0350	167.0360	5.99	*BP2, BCM2, BCD2
30	5-(3’,4’-dihydroxyphenyl)-valeric acid	C11H14O4	26.799	[M − H]−	210.0892	209.0819	209.0837	8.61	BCD1
31	2-Hydroxy-2-phenylacetic acid	C8H8O3	31.794	[M + H]+	152.0473	153.0546	153.0541	− 3.27	*BP1, BCD1
32	Phenacetylglycine	C10H11NO3	32.249	[M − H]−	193.0739	192.0666	192.0675	4.69	BCD2
Hydroxyphenylpropanoic acids
33	Dihydroferuloylglycine	C12H15NO5	26.826	[M + H]+	253.0950	254.1023	254.1012	− 4.33	BCD1
34	3-Methoxyacetophenone	C9H10O2	77.515	[M + H]+	150.0681	151.0754	151.0754	0.00	BCD1
35	3-Hydroxyphenylpropionic acid	C9H10O3	79.587	[M + H]+	166.0630	167.0703	167.0693	− 5.99	*BCM2, BCD2
Hydroxyphenylpentanoic acids
36	3-Hydroxyphenylvaleric acid	C11H14O3	28.199	[M + H]+	194.0943	195.1016	195.1017	0.51	*BP1, BCD1
Flavonoids
Flavonols
37	Kaempferol 7-O-glucoside	C21H19O11	8.246	[M − H]−	447.0927	446.0854	446.0852	− 0.45	BCD2
38	Myricetin	C15H10O8	19.405	[M + H]+	318.0376	319.0449	319.0456	2.19	BCD2
39	Kaempferol 3-O-glucosyl-rhamnosyl-galactoside	C33H40O20	26.244	[M + H]+	756.2113	757.2186	757.2178	− 1.06	*BP2, BCM2, BCD2
40	Patuletin 3-O-glucosyl-(1- > 6)-[apiosyl(1- > 2)]-glucoside	C33H40O22	29.974	[M + H]+	788.2011	789.2084	789.2046	− 4.81	*BCM2, BCD2
41	Kaempferol 3,7-O-diglucoside	C27H30O16	32.641	[M − H]−/*[M + H]+	610.1534	611.1607	611.1581	− 4.25	*BCM1, BCD1
42	Kaempferol 3,7,4’-O-triglucoside	C33H40O21	32.658	[M − H]−/*[M + H]+	772.2062	773.2135	773.2114	− 2.72	*BCM1, BCD1
43	Myricetin 3-O-rhamnoside	C21H20O12	39.662	[M + H]+	464.0955	465.1028	465.1036	1.72	*BP2, BCM1, BCD1
44	Patuletin 3-O-(2’’-feruloylglucosyl)(1- > 6)-[apiosyl(1- > 2)]-glucoside	C43H48O25	32.691	[M − H]−	964.2485	963.2412	963.2410	− 0.21	BCM1
45	Kaempferol 3-O-(2’’-rhamnosyl-galactoside) 7-O-rhamnoside	C33H40O19	41.733	[M + H]+	740.2164	741.2237	741.2247	1.35	*BP1, BCD1
46	Isorhamnetin 3-O-glucoside7-O-rhamnoside	C28H32O16	52.144	[M − H]−	624.1690	623.1617	623.1620	0.48	BP1
Anthocyanins
47	Malvidin 3,5-O-diglucoside	C29H35O17	6.750	[M + H]+	655.1874	656.1947	656.1945	− 0.30	BCM1
48	Delphinidin 3-O-glucosyl-glucoside	C27H31O17	15.088	[M − H]−	627.1561	626.1488	626.1497	1.44	*BP1, BCM1
49	Cyanidin 3,5-O-diglucoside	C27H31O16	23.238	[M − H]−	611.1612	610.1539	610.1531	− 1.31	*BP2, BCD2
50	Peonidin 3-O-sambubioside-5-O-glucoside	C33H41O20	26.088	[M − H]−	757.2191	756.2118	756.2130	1.59	*BP1, BCM1
51	Cyanidin 3-O-rutinoside	C27H31O15	26.800	[M − H]−	595.1663	594.1590	594.1587	− 0.50	*BP2, BCD2
52	Delphinidin 3-O-glucoside	C21H21O12	29.516	[M − H]−	465.1033	464.0960	464.0955	− 1.08	BCD1
53	Cyanidin 3-O-diglucoside-5-O-glucoside	C33H41O21	32.575	[M − H]−	773.2140	772.2067	772.2091	3.11	BCM1
54	Pelargonidin 3-O-sambubioside	C26---H29O14	43.647	[M − H]−	565.1557	564.1484	564.1485	0.18	BP1
55	Cyanidin 3-O-(2-O-(6-O-(E)-caffeoyl-Dglucoside)-D-glucoside)-5-O-D-glucoside	C43H49O24	43.84	[M − H]−	949.2614	948.2541	948.2547	0.63	BCM1
56	Peonidin 3-O-rutinoside	C28H33O15	46.512	*[M − H]−/[M + H]+	609.1819	608.1746	608.1730	− 2.63	*BP2, BCM2, BCD2
57	Pelargonidin 3-O-rutinoside	C27H31O14	53.900	[M − H]−	579.1714	578.1641	578.1635	− 1.04	BP2
Isoflavonoids
58	3’,4’,7-Trihydroxyisoflavan	C15H14O4	6.618	[M − H]−	258.0892	257.0819	257.0808	− 4.28	BCM1
59	Sativanone	C17H16O5	13.705	[M + H]+	300.0998	301.1071	301.1077	1.99	BP2
60	3’-O-Methylequol	C16H16O4	16.855	[M + H]+	272.1049	273.1122	273.1138	5.86	BCM1
61	2’-Hydroxyformononetin	C16H12O5	18.710	[M + H]+	284.0685	285.0758	285.0740	− 6.31	BCM1
62	3’,4’,7-Trihydroxyisoflavanone	C15H12O5	21.673	[M + H]+	272.0685	273.0758	273.0750	− 2.93	*BP2, BCM2
63	6’’-O-Acetyldaidzin	C23H22O10	25.055	[M − H]−	458.1213	457.1140	457.1126	− 3.06	BCM1
64	3’,4’,5,7-Tetrahydroxyisoflavanone	C15H12O6	26.645	[M + H]+	288.0634	289.0707	289.0712	1.73	BCM1
65	6’’-O-Acetylgenistin	C23H22O11	26.990	[M + H]+	474.1162	475.1235	475.1213	− 4.63	BP1
66	Irilone	C16H10O6	29.923	[M + H]+	298.0477	299.0550	299.0530	− 6.69	BCD2
67	Quercetin	C15H10O7	67.231	[M + H]+	302.0427	303.0500	303.0507	2.31	BP2, *BCM1, BCD1
68	3’-Hydroxymelanettin	C16H12O6	46.671	[M + H]+	300.0634	301.0707	301.0694	− 4.32	BCD2
69	3’-Hydroxydaidzein	C15H10O5	52.235	[M + H]+	270.0528	271.0601	271.0592	− 3.32	BP2
70	4’-Methoxy-2’,3,7-trihydroxyisoflavanone	C16H14O6	66.291	[M − H]−	302.0790	301.0717	301.0742	8.30	BCD1
71	Kaempferol	C15H10O6	79.891	*[M − H]−/[M + H]+	286.0477	285.0404	285.0411	2.46	*BP2, BCM2, BCD2
Flavones
72	Cirsilineol	C18H16O7	18.694	[M − H]−	344.0896	343.0823	343.0839	4.66	BCM2
73	Luteolin 7-O-glucuronide	C21H18O12	22.145	[M − H]−	462.0798	461.0725	461.0734	1.95	BCD1
74	Gardenin B	C19H18O7	25.088	[M + H]+	358.1053	359.1126	359.1120	− 1.67	BCM2
75	Apigenin 6,8-di-C-glucoside	C27H30O15	26.990	[M − H]−/*[M + H]+	594.1585	595.1658	595.1633	− 4.20	*BP2, BCM2, BCD2
76	Diosmin	C28H32O15	46.512	*[M − H]−	608.1741	607.1668	607.1693	4.12	*BP2, BCM2, BCD2
77	Apigenin 7-O-apiosyl-glucoside	C26H28O14	31.613	[M + H]+	564.1479	565.1552	565.1557	0.88	BCD2
78	Kaempferol-3-glucoside	C21H20O11	45.874	*[M + H]+	448.1006	449.1079	449.1076	− 0.67	BP2, *BCM1, BCD2
79	Isorhoifolin	C27H30O14	35.306	[M + H]+	578.1636	579.1709	579.1688	− 3.63	*BP2, BCD2
80	Apigenin 6-C-glucoside	C21H20O10	35.289	[M + H]+	432.1056	433.1129	433.1129	0.00	*BP2, BCD2
81	Chrysoeriol 7-O-glucoside	C22H22O11	46.604	[M + H]+	462.1162	463.1235	463.1235	0.00	BCD1
Flavanones
82	6-Geranylnaringenin	C25H28O5	7.584	[M − H]−	408.1937	407.1864	407.1882	4.42	*BP1, BCD1
83	Naringin	C27H32O14	41.270	[M + H]+	580.1792	581.1865	581.1842	− 3.96	BCD2
84	Hesperidin	C28H34O15	45.477	[M + H]+	610.1898	611.1971	611.1967	− 0.65	*BP2, BCD2
Flavanols
85	3’-O-Methyl-(-)-epicatechin7-O-glucuronide	C22H24O12	42.246	[M + H]+	480.1268	481.1341	481.1323	− 3.74	BP1
86	3’-O-Methylcatechin	C16H16O6	52.916	[M + H]+	304.0947	305.1020	305.1001	− 6.23	BCD1
Dihydrochalcones
87	3-Hydroxyphloretin2’-O-xylosyl-glucoside	C26H32O15	30.113	[M − H]−	584.1741	583.1668	583.1700	5.49	BP1
88	Phloretin 2’-O-xylosyl-glucoside	C26H32O14	43.061	[M + H]+	568.1792	569.1865	569.1865	0.00	BCM1
Dihydroflavonols
89	Dihydroquercetin 3-O-rhamnoside	C21H22O11	20.268	[M − H]−	450.1162	449.1089	449.1115	5.79	BCM2
Lignans
Lignans
90	Schisandrin C	C22H24O6	15.845	[M − H]−	384.1573	383.1500	383.1483	− 4.44	BCM2
91	7-Hydroxysecoisolariciresinol	C22H30O5	29.262	[M + H]+	374.2093	375.2166	375.2198	8.53	BCM1
92	Sesaminol 2-O-triglucoside	C36H46O22	34.365	[M − H]−	830.2481	829.2408	829.2393	− 1.81	BCM1
93	7-Oxomatairesinol	C20H20O7	39.648	[M + H]+	372.1209	373.1282	373.1283	0.27	BCM2
94	1-Acetoxypinoresinol	C22H24O8	50.065	[M + H]+	416.1471	417.1544	417.1542	− 0.48	BP2
95	Lariciresinol-sesquilignan	C30H36O10	52.536	[M − H]−	556.2308	555.2235	555.2265	5.40	BCM2
96	Episesamin	C20H18O6	62.591	[M − H]−	354.1103	353.1030	353.1055	7.08	BCM2
97	Arctigenin	C21H24O6	74.697	[M + H]+	372.1573	373.1646	373.1640	− 1.61	BP2
98	Schisandrin	C24H32O7	76.735	[M + H]+	432.2148	433.2221	433.2219	− 0.46	BP2
99	Schisanhenol	C23H30O6	76.901	[M + H]+	402.2042	403.2115	403.2111	− 0.99	BP2
100	Cyclolariciresinol	C20H24O6	77.398	[M − H]−/*[M + H]+	360.1573	361.1646	361.1645	− 0.28	*BP2, BCM2
101	Conidendrin	C20H20O6	77.515	[M + H]+	356.1260	357.1333	357.1321	− 3.36	BCD2
102	Matairesinol	C20H22O6	80.819	[M − H]−	358.1416	357.1343	357.1336	− 1.96	BP2
103	Dimethylmatairesinol	C22H26O6	81.274	[M + H]+	386.1729	387.1802	387.1787	− 3.87	BP1
104	Schisandrin B	C23H28O6	81.357	[M + H]+	400.1886	401.1959	401.1948	− 2.74	BP2
Other polyphenols
Tyrosols
105	Hydroxytyrosol 4-O-glucoside	C14H20O8	9.671	[M − H]−	316.1158	315.1085	315.1113	8.89	*BP2, BCM2
106	Hydroxytyrosol	C8H10O3	9.832	[M − H]−	154.0630	153.0557	153.0547	− 6.53	BCM2
107	Oleosidedimethylester	C18H26O11	14.470	[M − H]−	418.1475	417.1402	417.1421	4.55	BCM1
108	Oleuropein	C25H32O13	21.880	[M − H]−	540.1843	539.1770	539.1798	5.19	BCD2
109	3,4-DHPEA-AC	C10H12O4	23.255	*[M − H]−/[M + H]+	196.0736	195.0663	195.0672	4.61	*BP2, BCM2, BCD2
110	Ligstroside-aglycone	C19H22O7	30.609	[M − H]−	362.1366	361.1293	361.1312	5.26	BCD2
111	p-HPEA-AC	C10H12O3	81.340	[M − H]−/*[M + H]+	180.0786	181.0859	181.0852	− 3.87	*BP2, BCD2
Hydroxycoumarins
112	Scopoletin	C10H8O4	11.836	[M − H]−/*[M + H]+	192.0423	193.0496	193.0487	− 4.66	*BCM2, BCD2
113	Mellein	C10H10O3	19.014	*[M − H]−/[M + H]+	178.0630	177.0557	177.0566	5.08	*BP2, BCD2
114	Coumarin	C9H6O2	26.660	[M + H]+	146.0368	147.0441	147.0432	− 6.12	BCD2
115	4-Hydroxycoumarin	C9H6O3	49.073	[M + H]+	162.0317	163.0390	163.0379	− 6.75	BCD2
116	Esculetin	C9H6O4	78.510	[M + H]+	178.0266	179.0339	179.0335	− 2.23	BCM2
Hydroxybenzaldehydes
117	p-Anisaldehyde	C8H8O2	24.514	*[M − H]−	136.0524	135.0451	135.0448	− 2.22	*BP2, BCM2, BCD2
Hydroxybenzoketones
118	3-Hydroxy-3-(3-hydroxyphenyl) propionicacid	C9H10O4	33.766	[M + H]+	182.0579	183.0652	183.0645	− 3.82	BCD1
119	2,3-Dihydroxy-1-guaiacylpropanone	C10H12O5	50.529	[M + H]+	212.0685	213.0758	213.0751	− 3.29	*BP1, BCD1
Hydroxyphenylpropenes
120	Acetyleugenol	C12H14O3	62.774	[M − H]−	206.0943	205.0870	205.0884	6.83	BCM2
Alkylphenols
121	3-Methylcatechol	C7H8O2	10.566	*[M − H]−/[M + H]+	124.0524	123.0451	123.0455	3.25	*BP2, BCM2, BCD2
122	4-Vinylphenol	C8H8O	34.353	[M − H]−	120.0575	119.0502	119.0512	8.40	BCD1
Alkylmethoxyphenols
123	4-Ethylguaiacol	C9H12O2	19.125	[M − H]−	152.0837	151.0764	151.0774	6.62	*BCM2, BCD2
Naphtoquinones
124	1,4-Naphtoquinone	C10H6O2	26.380	[M + H]+	158.0368	159.0441	159.0444	1.89	BCM2
125	Juglone	C10H6O3	82.367	[M + H]+	174.0317	175.0390	175.0396	3.43	*BP2, BCM2
Phenolic terpenes
126	Rosmanol	C20H26O5	34.563	[M + H]+	346.1780	347.1853	347.1834	− 5.47	BCM2
127	Thymol	C10H14O	69.678	[M + H]+	150.1045	151.1118	151.1113	− 3.31	BP2
Curcuminoids
128	Demethoxycurcumin	C20H18O5	47.666	[M + H]+	338.1154	339.1227	339.1227	0.00	BCM2
Other polyphenols
129	Pyrogallol	C6H6O3	8.788	[M + H]+	126.0317	127.0390	127.0389	− 0.79	*BCM2, BCD2
130	3,4-Dihydroxyphenylglycol	C8H10O4	9.003	[M + H]+	170.0579	171.0652	171.0651	− 0.58	*BCM2, BCD2
131	Catechol	C6H6O2	17.551	[M + H]+	110.0368	111.0441	111.0435	− 5.40	BCM2
132	Arbutin	C12H16O7	21.772	[M + H]+	272.0896	273.0969	273.0951	− 6.59	BP2
133	Isopropyl 3-(3,4-dihydroxyphenyl)-2-hydroxypropanoate	C12H16O5	29.582	[M − H]−	240.0998	239.0925	239.0919	− 2.51	BCD1
134	Salvianolic acid C	C26H20O10	43.971	[M + H]+	492.1056	493.1129	493.1104	− 5.07	BCD2
Non-phenolic metabolites
135	Vanilloylglycine	C10H11NO5	6.541	[M − H]−	225.0637	224.0564	224.0563	− 0.45	BP2
136	1,3,5-Trimethoxybenzene	C9H12O3	57.471	[M + H]+	168.0786	169.0859	169.0844	− 8.87	BCD2
Stilbenes
Stilbenes
137	3’-Hydroxy-3,4,5,4’-tetramethoxystilbene	C17H18O5	27.192	[M − H]−	302.1154	301.1081	301.1100	6.31	BCM2
138	Resveratrol	C14H12O3	17.435	[M + H]+	228.0786	229.0859	229.0869	4.37	BCM2

*Example sample used for the LC-ESI-QTOF/MS parameters gathering for each phenolic compound in the selected mode

BP black pepper, BCM black cumin, BCD Black cardamom

¹Compounds identified first time in a particular black specie sample but already been reported in other plant materials including fruits, vegetables and medicinal plants

²Compounds already been identified in a particular black specie sample