Table 3.

LC-MS/MS characterization of phenolic metabolites in Australian native fruits and spices.

No.	Proposed Compounds	Molecular Formula	RT (min)	ESI +/−	Theoretical (m/z)	Observed (m/z)	Mass Error (ppm)	MS/MS	Samples
	Phenolic acids
	Hydroxybenzoic acids and derivatives
1	Gallic acid 4-O-glucoside	C13H16O10	5.212	[M−H]−	331.0671	331.0676	1.5	169, 125	MPB
2	Gallic acid	C7H6O5	6.288	[M−H]−	169.0142	169.0140	−1.2	125	MPB, SBG, R
3	Protocatechuic acid 4-O-glucoside	C13H16O9	8.861	[M−H]−	315.0721	315.0699	−7.0	153, 109	R, MPB
4	Protocatechuic acid	C7H6O4	9.341	[M−H]−	153.0193	153.0179	−9.1	109	MPB, SBG, R
5	p-Hydroxybenzoic acid	C7H6O3	12.359	[M−H]−	137.0244	137.0244	0.0	93	R, MPB
6	3-O-Methylgallic acid	C8H8O5	14.708	[M−H]−	183.0299	183.0296	−1.6	168, 124, 78	R, SBG
7	Benzoic acid	C7H6O2	26.507	[M−H]−	121.0295	121.0300	4.1	77	R, LA, SBG, MBP
8	4-Hydroxybenzoic acid 4-O-glucoside	C13H16O8	35.326	[M−H]−	299.0772	299.0773	0.3	255, 137	SBG, R
	Cinnamic acids and derivatives
9	3-Feruloyquinic acid lactone	C17H18O8	3.926	[M−H]−	349.0929	349.0921	−2.3	193, 191, 178	SBG
10	p-Coumaroyl malic acid	C13H12O7	4.495	[M−H]−	279.0510	279.0503	−2.5	163	LA, SBG
11	Ferulic acid 4-O-glucuronide	C16H18O10	6.585	[M−H]−	369.0827	369.0828	0.3	193	R, MPB, SBG, LA
12	1-O-Caffeoyl-ꞵ-D-glucose	C15H18O9	13.291	[M−H]−	341.0873	341.0870	−0.9	179, 135	SBG
13	Feruloyl tartaric acid	C14H14O9	14.091	[M−H]−	325.0565	325.0562	−0.9	193, 149, 105	SBG
14	Rosmarinic acid	C18H16O8	14.395	[M−H]−	359.0772	359.0753	−5.3	197, 179, 135	MPB
15	trans p-Coumaric acid 4-glucoside	C15H18O8	15.213	[M−H]−	325.0929	325.0926	−0.9	163, 119	SBG, LA, MPB
16	3-Caffeoylquinic acid	C16H18O9	15.691	[M−H]−	353.0878	353.0875	−0.8	191, 179, 161, 135	R, SBG, LA, MPB
17	Caffeic acid	C9H8O4	16.614	[M−H]−	179.0350	179.0343	−3.9	135	SBG, MPB, R, LA
18	Cinnamoyl glucose	C15H18O7	16.808	[M−H]−	309.0979	309.0979	0.0	147	R
19	1-O-Sinapoyl-ꞵ-D-glucose	C17H22O10	16.945	[M−H]−	385.1140	385.1139	−0.3	223	LA, MPB
20	Cinnamic acid	C9H8O2	17.423	[M−H]−	147.0451	147.0458	4.8	103	SBG, MPB
21	3-p-Coumaroylquinic acid	C16H18O8	18.518	[M−H]−	337.0929	337.0918	−3.3	191, 119	MPB, LA, R
22	3-Feruloylquinic acid	C17H20O9	19.200	[M−H]−	367.1034	367.1029	−1.4	191	R, LA
23	3-Sinapoylquinic acid	C18H22O10	21.997	[M−H]−	397.1140	397.1141	0.3	223, 191	LA, R
24	p-Coumaroyl tartaric acid	C13H12O8	22.056	[M−H]−	295.0459	295.0464	1.7	115	LA
25	p-Coumaric acid	C9H8O3	22.309	[M−H]−	163.0400	163.0400	0.0	119	R, LA, MPB
26	1,2-Disinapoylgentiobiose	C34H42O19	23.851	[M−H]−	753.2247	753.2247	0.0	223, 207	SBG, LA
27	Sinapic acid	C11H12O5	24.062	[M−H]−	223.0612	223.0618	2.7	193, 179, 149, 134	LA
28	Feruloyl glucose	C16H20O9	26.100	[M−H]−	355.1034	355.1038	1.1	223, 207	LA, MPB
29	1,2-Diferuloylgentiobiose	C32H38O17	26.359	[M−H]−	693.2036	693.2042	0.9	193, 134	LA, MPB, SBG
30	1,5-Dicaffeoylquinic acid	C25H24O12	26.770	[M−H]−	515.1195	515.1197	0.4	191, 179, 135	R, SBG
31	p-Coumaroyl glycolic acid	C11H10O5	60.679	[M+H]+	223.0601	223.0605	1.8	205, 147, 119	R, MPB
	Flavonoids
	Anthocyanins
32	Delphinidin 3-O-sambubioside	C26H29O16	11.988	[M]+	597.1456	597.1471	2.5	303	R, MBP
33	Cyanidin 3-sambubioside	C26H29O15	13.177	[M]+	581.1506	581.1526	3.4	287	R
34	Cyanidin	C15H11O6	13.926	[M]+	287.0556	287.0522	−11.8	231, 139, 69	MPB, R
35	Cyanidin 3-rutinoside	C27H31O15	13.621	[M]+	595.1663	595.1660	−0.5	287	MPB
36	Cyanidin 3-O-glucoside	C21H21O11	14.461	[M]+	449.1084	449.0994	20.4	287	MPB, R
37	Peonidin 3-O-(6″-p-coumaroyl-glucoside)	C31H29O13	16.378	[M]+	609.1608	609.1617	1.5	301	MPB
38	Delphinidin 3-rutinoside	C27H31O16	20.460	[M]+	611.1612	611.1623	1.8	449, 303	R
39	Delphinidin 3-galatoside	C21H21O12	20.460	[M]+	465.1033	465.1033	0.0	303	R
40	Delphinidin 3-O-(6″-p-coumaroyl-glucoside)	C30H27O14	20.528	[M]+	611.1401	611.1430	4.7	303	MPB, R
41	Delphinidin	C15H11O7	20.528	[M]+	303.0505	303.0495	−3.3	303	MPB, R
	Flavanols
42	Theaflavin 3-O-gallate	C36H28O16	4.172	[M+H]+	717.1450	717.1418	−4.5	699, 565, 139	SBG
43	Prodelphinidin trimer GC-GC-C	C45H38O20	6.333	[M−H]−	897.1883	897.1906	2.6	879, 305, 289, 125	SBG, R
44	(−)-Epigallocatechin	C15H14O7	12.207	[M−H]−	305.0667	305.0650	−5.6	289, 245, 179	R
45	4′,4″-Dimethylepigallocatechin gallate	C24H22O11	13.524	[M−H]−	485.1089	485.1092	0.6	441, 319, 183, 139	SBG
46	(−)-Epicatechin	C15H14O6	15.19	[M−H]−	289.0717	289.0711	−2.1	245, 205	SBG, R, MPB,
47	Cinnamtannin A2	C60H50O24	17.559	[M−H]−	1153.2619	1153.2602	−1.5	1135, 577, 289, 125	SBG
48	Catechin 3′-glucoside	C21H24O11	20.08	[M−H]−	451.1246	451.1253	1.6	289, 245	LA, MPB
	Flavanones
49	Naringin 6′-malonate	C30H34O17	3.858	[M−H]−	665.1723	665.1701	−3.3	579	SBG
50	6″-Acetylliquiritin	C23H24O10	6.288	[M−H]−	459.1297	459.1313	3.5	441, 255	SBG, R
51	Narirutin 4′-O-glucoside	C33H42O19	20.803	[M−H]−	741.2247	741.2269	3.0	579, 271	LA, SBG
52	Hesperetin 5-glucoside	C22H24O11	23.183	[M−H]−	463.1246	463.1252	1.3	301	LA
53	Hesperetin 3′-O-glucuronide	C22H22O12	23.249	[M−H]−	477.1038	477.1052	2.9	301	SBG, LA
54	6-Geranylnaringenin	C25H28O5	23.288	[M−H]−	407.1864	407.1864	0.0	287, 271	SBG
55	Naringenin-7-O-glucoside	C21H22O10	25.833	[M−H]−	433.1135	433.1154	4.4	301, 271, 151, 119	MPB, SBG
56	Eriodictyol-7-O-glucoside	C21H22O11	27.312	[M−H]−	449.1084	449.1046	−8.5	287, 151	SBG
57	Hesperetin	C16H14O6	27.569	[M−H]−	301.0717	301.0719	0.7	265, 221, 177, 137	LA, SBG, MPB
58	Hesperetin 5′,7-O-diglucuronide	C28H30O18	37.143	[M−H]−	653.1359	653.1341	−2.8	301	LA
59	Eriodictyol	C15H12O6	37.692	[M−H]−	287.0556	287.0572	5.6	151, 135	SBG
60	Naringenin	C15H12O5	43.436	[M−H]−	271.0607	271.0623	5.9	227, 151, 119, 107	SBG
61	8-Prenylnaringenin	C20H20O5	49.532	[M−H]−	339.1238	339.1230	−2.4	221, 147	MPB
62	5,7-Dihydroxyflavanone	C15H12O6	52.05	[M−H]−	255.0658	255.0671	5.1	213, 151	SBG
63	Hesperidin	C28H34O15	53.498	[M+H]+	611.1971	611.1966	−0.8	303	SBG
64	3′,4′,5′-Trimethoxyflavone	C18H16O5	56.326	[M−H]−	311.0920	311.0890	−9.6	296, 267	SBG
	Flavones and isoflavones
65	3′-O-Methylmaysin	C28H30O14	3.942	[M−H]−	589.1563	589.1571	1.4	589	R, LA
66	Tetramethylscutellarein	C19H18O6	5.213	[M−H]−	341.103	341.1030	0.0	341	R, MPB
67	Velutin	C17H14O6	6.265	[M−H]−	313.0717	313.0713	−1.3	313	SBG
68	Diosmin	C28H32O15	16.891	[M−H]−	607.1668	607.1669	0.2	301	MPB, LA
69	Azaleatin 3-arabinoside	C21H20O11	21.170	[M−H]−	447.0928	447.0903	−5.6	299, 269	MBP
70	Syringetin-3-O-glucoside	C23H24O13	24.105	[M−H]−	507.1144	507.1160	3.2	345	LA
71	Luteolin	C15H10O6	28.520	[M−H]−	285.0404	285.0423	6.7	267, 175, 133, 107	LA, MBP, R
72	Biochanin A 7-O-glucoside	C22H22O10	31.319	[M−H]−	445.1135	445.1156	4.7	283	SBG
73	Apigenin 6-C-glucoside	C21H20O10	32.237	[M−H]−	431.0983	431.0967	-3.7	271	MPB
74	Apigenin	C15H10O5	38.457	[M−H]−	269.0450	269.0467	6.3	225, 149	MPB
75	Chrysoeriol 7-O-glucoside	C22H22O11	40.140	[M−H]−	461.1089	461.1068	−4.6	299	MPB
76	Diosmetin	C16H12O6	40.251	[M−H]−	299.0561	299.0567	2.0	284, 265, 133	LA, MPB
77	Wogonin	C16H12O5	51.656	[M−H]−	283.0607	283.0587	−7.1	268	MPB
78	Glycitein	C16H12O5	52.368	[M−H]−	283.0607	283.0617	3.5	268	MPB
79	Chrysin	C15H10O4	52.451	[M−H]−	253.0501	253.0515	5.5	253	SBG
	Flavonols and dihydroflavonols
80	6-Hydroxykaempferol 3,6-diglucoside 7-glucuronide	C33H38O23	14.082	[M−H]−	801.1726	801.1826	12.5	447, 285	MBP
81	Limocitrin	C17H14O8	17.162	[M−H]−	345.0616	345.0604	−3.5	330, 315, 301, 181	LA
82	Myricetin 3-O-glucoside	C21H20O13	19.041	[M−H]−	479.0831	479.0816	−3.1	317	R
83	Quercetin 3-(2-galloylglucoside)	C28H24O16	20.371	[M−H]−	615.0986	615.0936	−8.1	301, 169	SBG
84	* Rutin	C27H30O16	20.530	[M−H]−	609.1461	609.1443	−3.0	301, 300, 271, 255	MPB, R
85	Myricetin 3-O-rhamnoside (myricitrin)	C21H20O12	21.328	[M−H]−	463.0882	463.0849	−7.1	317	SBG, R
86	Kaempferol 3-rutinoside	C27H30O15	24.911	[M−H]−	593.1507	593.1511	0.7	285, 151	MPB
87	Kaempferol 3-O-arabinoside	C20H18O10	25.902	[M−H]−	417.0822	417.0793	−7.0	285	MPB
88	Quercetin 3-rhamnoside (quercitrin)	C21H20O11	26.142	[M−H]−	447.0928	447.0941	2.9	301	SBG
89	Dihydroquercetin 3-O-rhamnoside	C21H22O11	26.305	[M−H]−	449.1089	449.1095	1.3	303	SBG, MPB
90	Quercetin 3-O-arabinoside	C20H18O11	25.269	[M−H]−	433.0776	433.0769	−1.6	301, 271, 151	MPB
91	Isorhamnetin 3-O-glucoside 7-O-rhamnoside	C28H32O16	26.574	[M−H]−	623.1617	623.1607	−1.6	315	R, LA
92	* Quercetin-3-O-glucoside	C21H20O12	27.258	[M−H]−	463.0882	463.0842	−8.6	301, 271, 255, 151	SBG, MBP, R
93	* Isorhamnetin	C16H12O7	29.384	[M−H]−	315.0510	315.0491	−6.0	300, 271, 151	LA, MPB, SBG
94	Kaempferol 3-O-glucoside	C21H20O11	30.214	[M−H]−	447.0928	447.0927	−0.2	285, 255, 147	MPB, R, LA
95	* Myricetin	C15H10O8	30.613	[M−H]−	317.0298	317.0314	3.3	179, 151	SBG, MPB, R
96	* Taxifolin	C15H12O7	31.176	[M−H]−	303.0510	303.0505	−1.7	217, 125	LA, MPB
97	Isorhamnetin 3-O-glucuronide	C22H20O13	31.344	[M−H]−	491.0831	491.0819	−2.4	315	R
98	* Quercetin	C15H10O7	39.148	[M−H]−	301.0353	301.0352	−0.3	271, 179, 151, 121	SBG, LA, MPB, R
	Chalcones
99	Xanthohumol	C21H22O5	10.842	[M−H]−	353.1389	353.1399	2.8	295, 233	SBG
100	Phloretin	C15H14O5	28.333	[M−H]−	273.0768	273.0780	4.3	167, 119	SBG
101	Phloretin-2′-O-glucoside	C21H24O10	28.33	[M−H]−	435.1296	435.1303	1.5	273, 167	SBG
	Isoflavonoids
102	Dihydroformononetin	C16H14O4	3.991	[M−H]−	269.0819	269.0816	−1.1	253, 239, 223	SBG, MPB
103	Equol 7-O-glucuronide	C21H22O9	6.310	[M−H]−	417.1191	417.1201	2.4	241	SBG
104	6″-O-Malonyldaidzin	C24H22O12	14.474	[M−H]−	501.1038	501.1027	−2.2	415	MPB, LA
105	6″-O-Acetyldaidzin	C23H22O10	16.980	[M−H]−	457.1140	457.1138	−0.4	415	SBG, R
106	Daidzin 4′-O-glucuronide	C27H28O15	21.029	[M−H]−	591.1355	591.1353	−0.3	415, 253	LA, R, SBG
107	3′,4′,7-Trihydroxyisoflavanone	C15H12O5	27.308	[M−H]−	271.0612	271.0611	−0.4	239, 135, 121	SBG
108	3′-O-Methylviolanone	C18H18O6	27.762	[M−H]−	329.1030	329.1029	−0.3	285, 163	MPB, LA
109	Daidzein 7-O-glucuronide	C21H18O10	33.742	[M−H]−	429.0827	429.0807	−4.7	253	R
110	3′-Hydroxymelanettin	C16H12O6	40.251	[M−H]−	299.0561	299.0567	2.0	284	LA, MPB
111	2′-Hydroxyformononetin	C16H12O5	52.124	[M−H]−	283.0612	283.0606	−2.1	268	SBG, MPB
	Tannins
112	Gallagic acid	C28H12O16	3.075	[M−H]−	603.0052	603.0041	−1.8	587, 559, 549, 446	R, MPB
113	2-O-Galloylpunicalin	C41H26O26	6.333	[M−H]−	933.0639	933.0645	0.6	781, 169, 125	SBG
114	Glucosyringic acid	C15H20O10	7.546	[M−H]−	359.0978	359.0914	−17.8	315, 197, 153, 125	MPB
115	Procyanidin trimer C1	C45H38O18	16.230	[M−H]−	865.1985	865.2012	3.1	739, 713, 695	SBG, R
116	Procyanidin B2	C30H26O12	19.039	[M−H]−	577.1351	577.1323	−4.9	451, 425, 289, 245	MPB, LA, SBG, R
117	Punicafolin	C41H30O26	19.102	[M−H]−	937.0952	937.0966	1.5	169, 125	SBG
118	Ellagic acid	C14H6O8	55.906	[M−H]−	300.9990	300.9988	−0.7	284, 257	LA, MBP, R
	Stilbenes
119	Piceatannol	C14H12O4	5.594	[M−H]−	243.0663	243.0653	−4.1	225, 201	SBG, MPB
120	Polydatin	C20H22O8	21.854	[M−H]−	389.1242	389.1245	0.8	227	LA, MPB, SBG
121	Piceatannol 3-O-glucoside	C20H22O9	30.064	[M−H]−	405.1191	405.1188	−0.7	243	MPB
	Lignans
122	Sesamin	C20H18O6	4.879	[M−H]−	353.1030	353.1015	−4.2	338, 163	MPB
123	2-Hydroxyenterolactone	C18H18O5	6.371	[M−H]−	313.1081	313.1091	3.2	255, 163	LA, MPB
124	Silibinin	C25H22O10	16.794	[M−H]−	481.1140	481.1151	2.3	301, 179, 165, 151	MPB
125	7-Oxomatairesinol	C20H20O7	21.997	[M−H]−	371.1136	371.1138	0.5	358, 343, 328	LA
126	Arctigenin	C21H24O6	23.288	[M−H]−	371.1500	371.1497	−0.8	356, 312, 295	SBG
127	Enterolactone	C18H18O4	47.739	[M−H]−	299.1288	299.1299	4.3	281, 187, 165	MPB, SBG
128	2-Hydroxyenterodiol	C18H22O5	53.013	[M−H]−	317.1394	317.1395	0.3	299, 287, 269, 257	MPB
	Other compounds
129	Pyrogallol	C6H6O3	7.009	[M−H]−	125.0244	125.0242	−1.6	107, 97, 79	MPB
130	[6]-Gingerol	C17H26O4	12.249	[M−H]−	293.1758	293.1768	3.4	137	SBG, MPB
131	Quinic acid	C7H12O6	4.189	[M−H]−	191.0561	191.0578	9.0	85	MPB, SBG
132	1,2,4,6-Tetragalloyl-ꞵ-D-glucopyranose	C34H28O22	19.144	[M−H]−	787.0999	787.0953	−5.9	169, 125	SBG
133	Umbelliferone	C9H6O3	19.396	[M−H]−	161.0244	161.0246	1.2	133	MPB, R
134	2-Hydroxybenzaldehyde	C7H6O2	20.620	[M−H]−	121.0269	121.0276	5.8	92, 77	MPB
135	p-Coumaraldehyde	C9H8O2	29.139	[M−H]−	147.0451	147.0463	8.0	119	MPB
136	Xanthotoxol	C11H6O4	47.927	[M−H]−	201.0193	201.0191	−1.0	171	MPB, LA, SBG
137	Carnosic acid	C20H28O4	55.899	[M−H]−	331.1915	331.1927	3.6	287	SBG, R
138	Mellein	C10H10O3	62.141	[M+H]+	179.0703	179.0694	−5.0	135	LA
	Limonoids
139	Limonin	C26H30O8	19.039	[M−H]−	469.1868	469.1859	−1.9	229	LA
140	Obacunoic acid	C26H32O8	25.201	[M−H]−	471.2024	471.2027	0.6	471	LA, MPB, SBG
141	Nomilin	C28H34O9	51.280	[M+H]+	515.2276	515.2280	0.8	515	MPB, SBG
142	Obacunone	C26H30O7	19.253	[M−H]−	455.2065	455.2065	0.0	407, 163	SBG, R, MPB, LA
143	Citrusin	C28H34O11	55.330	[M+H]+	547.2174	547.2162	−2.2	547	LA

Mountain pepper berries (MPB), rosella (R), lemon aspen (LA), and strawberry gum (SBG). Compounds with asterisk (*) were identified with pure standards.