. 2017 Jul 31;114(34):9062–9067. doi: 10.1073/pnas.1707176114

Table S1.

Betalains identified by LC-MS analysis

No.		Identified compound	Rt, min	[M + H], Da	λmax, nm	Elemental composition	Mass error, ppm	MS/MS fragments
pX11 tobacco flower
1		Glutamine-Bx	2.43	340.1148	469	C14H17N3O7	0.6	323.08 [M+H-NH3]
								277.08 [M+H-NH3-H2COO]
								231.07 [M+H-NH3-2xH2COO]
								194.04 [M+H-C5H10N2O3]
								185.07 [M+H-3xH2COO-NH3]
								150.05 [M+H-COO-C5H10N2O3]
								148.05 [M+H-H2COO-C5H10N2O3]
								130.05
2		Proline-Bx	7.76	309.1087	478
3		Betanin	8.30	551.1513	534	C24H26N2O13	0.0	389.10 [M+H-Hex]
								345.11 [M+H-Hex-COO]-
								343.09 [M+H-Hex-H2COO]
								297.09 [M+H-Hex-2xH2COO]
								150.1 [M+H-Hex-H2COO-C9H7NO4]
4		Isobetanin	9.04	551.1502	533	C24H26N2O13	2.0	389.10 [M+H-Hex]
								345.11 [M+H-Hex-COO]-
								343.09 [M+H-Hex-H2COO]
								297.09 [M+H-Hex-2xH2COO]
								150.1 [M+H-Hex-H2COO-C9H7NO4]
5		Tyramine-Bx	11.96	331.13	464	C17H18 N2O5	1.8	287.14 [M+H-COO]
								211.07 [M+H-C8H9O]
								121.06 [M+H-C9H10N2O4]
pX12 tobacco flower
1		Aspargine-Bx	1.59	326.0922	470
2		Glutamine-Bx	2.42	340.1148	470
3		Proline-Bx	7.76	309.1088	478
4		Betanin	8.30	551.1516	534
5		Isobetanin	9.04	551.1517	533
6		Tyramine-Bx	11.96	331.1298	464
pX13 tobacco flower
1		Aspargine-Bx	1.60	326.0984	470	C13H15N3O7	1.2	309.07 [M+H-NH3]
								194.04 [M+H-C4H8N2O3]
								166.05 [M+H-C4H8N2O3-CO]
								124.04
2		Glutamine-Bx	2.42	340.1146	470
3		Proline-Bx	7.77	309.1089	478
4		Tyramine-Bx	11.97	331.1306	465
pX11 potato tuber
1		Aspargine-Bx	1.57	326.0991	469
2		Glutamine-Bx	2.36	340.1146	470
3		Betanin	8.34	551.1503	534
4		Isobetanin	9.01	551.1510	533
5		Valine-Bx	10.57	311.1246	472	C14H18N2O6	1.0	267.11 [M+H-COO]
								219.13 [M+H-2xH2COO]
								193.13
								175.12 [M+H-COO-2xH2COO]
								150.05
6		Unidentified Bc	11.26	656.1711	533
pX11 eggplant fruit
1		Unidentified Bx	6.5	369.1299	479	C16H20N2O8	0.3	351.12 [M+H-H₂O]
								237.09
								211.07
								150.05
3		Betanin	8.26	551.1508	533
4		Isobetanin	9.00	551.1509	534
5		Unidentified bc	11.27	656.1725	533	C30H29N3O14	0.5	612.18 [M+H-COO]
								568.19 [M+H-2xCOO]
								417.13 [betanidin+H+CH2CH2]
								389.10 [betanidin+H]
								345.10 [betanidin+H-COO]
								301.12 [betanidin+H-2xCOO] 268.08
6		Unidentified Bc	12.66	670.189	533	C31H31N3O14	0.9	626.20 [M+H-COO]
								582.21 [M+H-2xCOO]
								538.22 [M+H-3xCOO]
								389.10 [M+H-281.090 (C13H15NO6)]
								345.11 [M+H-281-COO]
								301.11 [M+H-281–2xCOO]
								282.09 [M+H-389.10 (Betanidin)]
								264.09 [M+H-betanidin-H₂O]
								257.13 [M+H-281–3xCOO]
								247.08
								180.10
								138.06
7		Unidentified Bc	15.63	655.1771	533	C31H30N2O14	0.8	389.10 [M+H-266.0790 (C13H14O6)]
								345.10 [M+H-266-COO]
								343.10 [M+H-266-H2COO]
								301.12 [M+H-266–2xCOO]
								299.10 [M+H-266-H2COO-COO]
								196.06 [M+H-C9H7NO4]
								194.04 [M+H-C9H9NO4]
								150.05 [M+H-266.0790-H2COO-C9H7NO4]
pX11 tomato fruit
1		Proline-Bx	7.72	309.109	478	C14H16N2O6	1.0	263.10 [M+H-H2COO]
								217.10 [M+H-2xH2COO]
								106.07 [M+H-2COO-C5H9NO2]
2		Betanin	8.26	551.1517	534
3		Isobetanin	9.00	551.1510	534
4		Betanidin	9.78	389.0985	539
5		Unidentified bc	17.75	835.2209	524	C40H38N2O18	1.3	551.15 [betanin+H]
								478.11 [M+H-195.05 (C9H9NO4)-162.05 (Hex)]
								434.12 [M+H-195.05 (C9H9NO4)-162.05 (Hex)-COO] 389.10 [betanidin+H]
								314.07
								285.07 [C16H12O5+H]
pX11-BY2 cells
1		Unidentified Bx	2.01	362.0851	466	C12H15N3O10	4.1	200.03
2		Glutamine-Bx	2.41	340.1139	469
3		Alanine-Bx	6.49	283.0934	468	C12H14N2O6	1.4	237.09 [M+H-H2COO]
								191.08 [M+H-2xH2COO]
								165.10
								150.05 [M+H-C3H7NO4-COO]
								145.08 [M+H-3xH2COO]
4		Bougainvillein-r-I	7.72	713.2039	530	C30H36N2O18	0.3	551.15 [M+H-Hex]
4		Bougainvillein-r-I	7.72	713.2039	530	C30H36N2O18	0.3	389.10 [M+H-2Hex]
5		Betanin	8.27	551.1520	533
6		Isobetanin	9.01	551.1515	535
pX13-BY2 cells
1		Glutamine-Bx	2.35	340.1148	470
2		Alanine-Bx	6.47	283.0931	468
pX11 Solanum nigrum fruit
1	Betanin		8.34	551.1514	535
2	2-Apiosyl-betanin		8.95	683.1938	535	C29H34N2O17	0.3	551.14 [M+H-C5H8O4 (Apiosyl)]
								389.09 [M+H-Apiosyl-Hex]
								345.11 [M+H-Apiosyl-Hex-COO]
								343.09 [M+H-Apiosyl-Hex-H2COO]
3	Isobetanin		9.08	551.1503	535
4	2-Apiosyl-isobetanin		9.66	683.1950	535	C29H34N2O17	2.0	551.14 [M+H-C5H8O4 (Apiosyl)]
								389.09 [M+H-Apiosyl-Hex]
								345.11 [M+H-Apiosyl-Hex-COO]
								343.09 [M+H-Apiosyl-Hex-H2COO]
5	Betanidin		9.89	389.0974	535	C18H16N2O8	2.8	345.11 [M+H-COO]
5	Betanidin		9.89	389.0974	535	C18H16N2O8	2.8	343.09 [M+H-H2COO]
6	Unidentified Bc		10.36	667.1989	535			389.10 [betanidin+H]
								345.10 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
7	Neobetanin		10.61	549.1353	465	C24H24N2O13	0.7	387.1 [M+H-Hex]
7	Neobetanin		10.61	549.1353	465	C24H24N2O13	0.7	341.0 [M+H-Hex-H2COO]
8	Isobetanidin		10.84	389.0986	535	C18H16N2O8	0.3
9	Unidentified Bc		11.06	637.1887	535	C28H32N2O15	0.9	389.10 [betanidin+H]
								345.10 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
10	Unidentified Bc		11.23	700.1995	535	C32H33N3O15	0.7	389.10 [betanidin+H]
								350.60
								343.09 [betanidin+H-H2COO]
								294.10
								168.07
11	2-Decarboxy-hylocerenin		11.63	651.2054	535	C29H34N2O15	2.6	389.10 [betanidin+H]
								345.11 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
12	Unidentified Bc		11.73	637.1890	535			389.10 [betanidin+H]
								345.10 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
13	Glucosyl-salicyl-betanin		12.04	833.2260	535	C37H40N2O20	0.8	671.17 [M+H-Hex]
14	Unidentified Bc		12.25	863.2360	535	C38H42N2O21	0.2	701.18 [M+H-Hex]
								389.10 [betanidin+H]
								345.11 [betanidin+H-COO]
15	Unidentified Bc		12.38	718.2092	535	C32H35N3O16	0.6	389.10 [betanidin+H]
16	Glucosyl-salicyl-isobetanin		12.57	833.2263	535	C37H40N2O20	1.2	671.17 [M+H-Hex]
17	Unidentified Bc		12.66	723.2254	535	C32H38N2O17	0.7	389.10 [betanidin+H]
18	Unidentified Bc		12.77	670.1904	535
19	Unidentified Bc		12.73	863.2361	535			701.18
								389.10 [betanidin+H]
								345.11 [betanidin+H-COO]
20	Unidentified Bc		13.05	718.2103	535			389.10 [betanidin+H]
21	Unidentified Bc		13.20	670.1885	535
22	Unidentified Bc		13.20	723.2288	535			389.10 [betanidin+H]
23	Salicyl-betanin		14.07	671.1722	535	C31H30N2O15	0.3	389.10 [betanidin+H]
								345.11 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
24	Unidentified Bc		14.35	701.1839	535	C32H32N2O16	1.3	389.09 [betanidin+H]
								345.11 [betanidin+H-COO]
								343.10 [betanidin+H-H2COO]
								196.0 [betanidin+H-C9H7NO4]
								194.04 [betanidin+H-C9H9NO4]
								150.05 [betanidin+H-H2CO2-C9H7NO4]
								106.0 [betanidin+H-H2CO2-C9H7NO4-CO₂)]
25	Salicyl-isobetanin		14.57	671.1736	535	C31H30N2O15	1.8	389.10 [betanidin+H]
								345.11 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
26	Unidentified Bc		14.78	701.1835	535	C32H32N2O16	0.7	389.09 [betanidin+H]
								345.11 [betanidin+H-COO]
								343.10 [betanidin+H-H2COO]
								196.0 [betanidin+H-C9H7NO4]
								194.04 [betanidin+H-C9H9NO4]
								150.05 [betanidin+H-H2CO2-C9H7NO4]
								106.0 [betanidin+H-H2CO2-C9H7NO4-CO₂)]
27	Sinapoyl-betanin		16.33	757.2087	535	C35H36N2O17	0.7	551.15 [betanin+H]
								345.11 [betanidin+H-COO]
								343.10 [betanidin+H-H2COO]
								301.12 [betanidin+H-2xCOO]
								207.06 [sinapic acid+H-H₂O]
								194.05 [betanidin+H-C9H9NO4]
								150.05 [betanidin+H-H2CO2-C9H7NO4]
28	Sinapoyl-isobetanin		16.55	757.2076	535	C35H36N2O17	2.1	551.15 [betanin+H]
								345.11 [betanidin+H-COO]
								343.09 [betanidin+H-H2COO]
								301.12 [betanidin+H-2xCOO]
								207.06 [sinapic acid+H-H₂O]
								194.04 [betanidin+H-C9H9NO4]
								150.05 [betanidin+H-H2CO2-C9H7NO4]

Betalains identified by LC-MS analysis. Assigned elemental composition with mass error and fragmentation patterns are given once for each compound to avoid redundancy. All fragments were obtained in the MS/MS mode. Rt, retention time; UV/VIS, absorption maxima at UV/visible range; Bc, betacyanin; Bx, betaxanthin; Hex, hexose.