Characterization, Classification and Authentication of Turmeric and Curry Samples by Targeted LC-HRMS Polyphenolic and Curcuminoid Profiling and Chemometrics

Supplementary Material Characterization, Classification and Authentication of Turmeric and Curry Samples by Targeted LC-HRMS Polyphenolic and Curcuminoid Profiling and Chemometrics

Nerea Núñez1,*, Oscar Vidal-Casanella1, Sonia Sentellas1, Javier Saurina1,2, and Oscar Núñez 1,2,3,* 1 Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Martí i Franquès 1-11, E08028 Barcelona, Spain; [email protected] (O. V.-C.); [email protected] (S.S.); [email protected] (J.S.) 2 Research Institute in Food Nutrition and Food Safety, University of Barcelona, Recinte Torribera, Av. Prat de la Riba 171, Edifici de Recerca (Gaudí), Santa Coloma de Gramenet, E08921 Barcelona, Spain 3 Serra Húnter Fellow, Generalitat de Catalunya, Rambla de Catalunya 19-21, E08007 Barcelona, Spain * Correspondence: [email protected] (N.N.), [email protected] (O.N.); Tel.: +34-93-403-3706

Table S1. HRMS curcuminoid accurate mass data base employed with TraceFinderTM software.

Compounds Chemical formula Tentative [M-H]- structure [M-H]- m/z calculated value

curcumin C21H20O6 367.11869

Dmc C20H18O5 337.10812 -

bdmc C19H16O4 307.09756 -

5 C19H16O5 323.09247

10 C20H18O6 353.10304

N1 C19H16O6 339.08739

1 C19H18O5 325.10812

2 and 3 C20H20O6 355.11869

6 C21H22O7 385.12925

4 C19H18O5 325.10812

9 C19H18O4 309.11321

N2 C20H20O5 339.12377

N3 C21H22O6 369.13434

N4 C20H20O6 355.11869

N5 C19H18O6 341.10304

N6 C19H18O5 325.10812

8 C19H16O3 291.10264

N7 C21H20O5 351.12377

N8 C20H18O5 337.10812

N9 C19H16O5 323.09247

N10 C19H16O4 307.09756

N11 C20H18O4 321.11321

7 C18H16O4 295.09756

For most of the compounds, both keto and enol tautormes can be present as shown below:

5 3 2 1 4 PC (7.64%) 2 5 7 on 0 8 6 10 11

9 Scores Scores -5 QC Samples -10 -10 -5 0 5 10 15 20 Scores on PC 1 (12.80%)

Figure S1. PCA score plot of PC1 vs. PC2 showing the behavior of QCs and analyzed samples when targeted LC-HRMS bioactive compound profiles were used as chemical descriptors. A total of 4 PCs were used to build the model.

57 58 54 8 62 32, 29 1 53 7 (a) 82 65 61, 64 Variable tR 68 procyanidin B2 6.27 0.25 84 66 1 D-(-)-Quinic acid 3.01 69 procyanidin B2 9.24 85 69 15 14 35 2 Ethyl gallate 3.81 70 Luteolin-7-O-b-D-glucuronide 5.73 0.2 4-o-Caffeoylquinic acid 20 51 3 Homovanillic acid 3.81 71 Luteolin-7-O-b-D-glucuronide 6.32 Chlorogenic acid 46 23 Nepetin-7-glucoside 48 50 10, 11 4 Syringaldehyde 3.81 72 Luteolin-7-O-b-D-glucuronide 10.55 Rutin 5 Syringic acid 3.81 73 Luteolin-7-O-b-D-glucuronide 12.42 D-(-)-Quinic acid 24, 26 83 67 0.15 Cirsimaritin 75 40 6 Veratric acid 3.81 74 Luteolin-7-O-b-D-glucuronide 13.22 Genkwanin 71 25, 27 Anemosapogein 2,5-Dihydroxybenzoic acid 7 2,5-Dihydroxybenzoic acid 3.82 75 procianidina A2 3.03 Quercitrin 70 49 Asiatic acid Rosmarinic acid 8 Caffeic acid 3.86 76 Myricetin 5.46 0.1 Carnosic acid 81 Hesperidin procyanidin B2 68 9 Sinapic acid 3.86 77 Betulinic acid 23.17 procianidina A24-Hydroxybenzoic acid Luteolin-7-O-b-D-glucuronide 10 3,4-Dihydroxybenzaldehyde 4.32 78 Betulinic acid 25.46 Arbutin 0.05 Rosmanol procyanidin B2 11 4-Hydroxybenzoic acid 4.32 79 Ursolic acid 23.17 Ursolic acid 12 Homogentisic acid 4.36 80 Ursolic acid 25.46 N9 22 2 i 3 10 13 Vanillic acid 4.36 81 Arbutin 3.02 0 Chlorogenic acid LV 2 (13.71%) LV 2 Myricetin 14 Ellagic acid 4.49 82 Genkwanin 12.51 6 Rutin 77, 79 6 N4 N3 15 Polydatin 4.58 83 Hesperidin 3.96 N5 6 CirsimaritinSyringic acid Quercitrin 55 106 -0.05 N7 72, 78 112 16 p-coumaric acid 5.11 84 Anemosapogein 19.43 N7 N4 135 80, 109 N9 bdmc 36 43 33 34 17 Ferulic acid 5.26 85 Asiatic acid 13.03 SinapicN2acid 73 60 30 76 3, 4, 6, 31 91 39, 92 18 Vanillin 5.45 86 1 6.41 -0.1 N11 N3Ferulic acid 63 41 97 56 Trans-Cinnamic acid 59 134 19 trans-Cinnamic acid 6.11 87 4 6.41 8 47 45 94 116 38 90 99 52 28 20 trans-Cinnamic acid 7.38 88 N6 6.41 curcumin 127 2, 5 -0.15 120 37 21 Rosmanol 6.55 89 N1 6.86 N8 42 96, 102, 110 105 22 Rosmanol 7.82 90 N1 7.23 111 93 121 122, 124, 108 98 23 Rosmanol 10.55 91 N4 7.92 -0.2 44 9 119 115 -0.3 -0.2 -0.1 0 0.1 0.2 131, 133 16 24 Morin 4.01 92 N4 9.26 LV 1 (23.56%) 17 25 Morin 7.12 93 N4 10.89 74, 95, 101 126 19 26 Quercetin 4.01 94 N4 11.26 114, 117, 12, 13, 89 100 27 Quercetin 7.12 95 7 9.19 18, 104, 86, 87, 88 118, 125, 113 28 Resveratrol 7.47 96 6 8.85 (b) 132, 135 107, 126 130 123 29 Fisetin 7.07 97 6 9.91 30 Fisetin 8.77 98 6 10.81 128, 129 82 21 31 Fisetin 9.33 99 6 11.16 66 32 Kaempferol 7.07 100 8 10.43 53 69 33 Kaempferol 8.77 101 N11 10.68 49 54 84 40 34 Kaempferol 9.33 102 N11 11.29 58 61 68 20 83 35 Quercitrin 4,00 103 5 9.44 57 85 62 120 36 Quercitrin 4.69 104 5 10.82 23 67, 68, 71 12, 13, 116 37 Quercitrin 10.95 105 5 11.42 8 50, 64 75 14, 25, 27 124 127 51 3, 4, 10, 46, 55, 60, 42 38 Quercitrin 11.49 106 N9 9.44 22 7 24, 26 72, 73, 74, 77, 78, 79, 34 105, 108 39 Quercitrin 12.68 107 N9 10.82 65 70 36 106 99 35 80, 91, 95, 103, 114, 102 111 40 Homoplantaginin 4.5 108 N9 11.38 15 128 112 117, 118, 125, 132 76 131 41 Homoplantaginin 8.06 109 N7 10.90 29, 32 135 94 113 129 74 109 42 Homoplantaginin 11.45 110 N7 11.44 1 48 43 Umbelliferon 11.67 111 N7 14.52 38 115 96 81 44 Umbelliferon 13.33 112 10 10.29 81 97 28 126 45 12-methoxycarnosic acid 17.13 113 10 11.14 119 92 52 43, 45, 104 46 12-methoxycarnosic acid 19.54 114 9 8.05 N2 37 63 93 47 Carnosic acid 17.13 115 9 12.27 Genkwanin N3 Homoplantaginin 133 123 48 Carnosic acid 19.58 6 5 47 101 116 9 13.00 Taxifolin N10 N9 56 110 21 Chlorogenic acid N7 30 49 Carnosol 18.07 117 N2 8.03 procyanidin B2 N11 45 9 130 Anemosapogein 10 N8 33, 50 Rosmarinic acid 3.83 118 N2 9.00 Carnosol curcumin 39 107 0.1 Rosmarinic acid procyanidin B2 96 13444 51 Rosmarinic acid 4.81 119 N2 12.54 Asiatic acid Quercitrin 88 Caffeic acid procyanidin B2 Resveratrol 122 121 89 52 Cirsimaritin 8.30 120 N2 13.14 (-)-Epicatechin N2 Luteolin-7-O-b-6D-glucuronide N3 53 Cirsimaritin 10.87 121 bdmc 12.80 (+)-catequina 9 59 procyanidin A2 N4 N4 6 18 54 Nepetin-7-glucoside 4.40 122 bdmc 13.47 UmbelliferonQuercitrin 31 Quercetin N5 19 100 55 Nepetin-7-glucoside 10.36 123 N10 12.70 Kaempferol Luteolin-7-O-b-D-glucuronide N10 2, 5 0 N5 N11 56 Nepetin-7-glucoside 12.70 124 N10 13.47 Rosmanol Carnosic acid curcumin 41 10 N9 Rosmanol 57 4-o-Caffeoylquinic acid 3.97 125 N3 8.67 D-(-)-Quinic acidN9 N7 Umbelliferon 99% 16 Nepetin-7-glucoside bdmcN1 104 6 58 Chlorogenic acid 3.97 126 N3 12.83 2 i 3 N6 Carnosic acid 17 59 Chlorogenic acid 9.93 127 N3 13.61 Veratric acid LV 4 (4.24%) LV 4 Arbutin 60 Chlorogenic acid 13.02 128 dmc 13.21 -0.1 Chlorogenic acid 8 61 Gallic acid 3.79 129 N8 13.01 Syringic acid Homoplantaginin 62 Rutin 3.65 130 curcumin 13.47 p-coumaric acid 63 Rutin 12.61 131 curcumin 14.05 Ferulic acid 64 (-)-Epicatechin 3.97 132 N5 5.89 -0.2 65 (+)-catechin 3.97 133 N5 6.66 0 66 Taxifolin 5.03 134 N5 7.49 -0.05 67 Procyanidin B2 5.59 135 2 i 3 2.89 0.2 LV 1 0.1 -0.1 0 (23.56%) LV 2 (13.71%) -0.15 -0.1 Figure S2. Enlargment of loadings plot depitect in Figure 3 with full name descriptios. (a) LV1 vs. LV2 and (b) LV1 vs. LV2 vs. LV3 when using corrected targeted LC-HRMS polyphenolic and curcuminoid profiles as sample chemical descriptors.

15 Turmeric samples Curry samples 10 QCs

0 Scores on PC 2 (18.32%)on Scores PC -5

-10 -10 -5 0 5 10 Scores on PC 1 (34.88%)

Figure S3. PCA score plot of PC1 vs. PC2 when only corrected targeted LC-HRMS curcuminoid profiles were used as sample chemical descriptors. A total of 4 PCs were employed to build the model.