Electronic Supplementary Material (ESI) for Food & Function. This Journal Is © the Royal Society of Chemistry 2016

Home , Chrysoeriol, Cirsilineol, Eriodictyol, Rhoifolin, Sakuranetin, Spinacetin

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Electronic Supplementary Material (ESI) for Food & Function. This journal is © The Royal Society of Chemistry 2016 O Supplementary8 7 6 5 4 3Table 2’ 3 ’1: 4 ’Flavonol 5’ 6’ compounds reported in the United States Department of Agriculture (USDA) 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ and Phenol-Explorer (PE) databases OH O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Compounds Compounds 8 7 6 5 4 3 2’ 3’ 4’ 1 5’ 6’ Aglycone structure reported in USDA reported in PE

HO O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

OH Galangin*; Methylgalangin

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO OH

8 7 HO6 5 4 O3 2’ 3’ 4’ 5’ 6’ 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

OH Morin*

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

Kaempferol*; Kaempferol 3,7,4'-O-triglucoside; Kaempferol 3,7-O-diglucoside; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Kaempferol 3-O-(2''-rhamnosyl-6''-acetyl-galactoside) 7-O-rhamnoside; Kaempferol

OH 3-O-(2''-rhamnosyl-galactoside) 7-O-rhamnoside; Kaempferol 3-O-(6"-malonyl-

glucoside) ; Kaempferol 7-O-glucoside; Kaempferol 3-O-(6''-acetyl-galactoside) 7-O- 8 7 HO6 5 4 O3 2’ 3’ 4’ 5’ 6’ 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ rhamnoside; Kaempferol 3-O-xylosyl-rutinoside; Kaempferol3-O-rutinoside;

OH r = 0.93 Kaempferol* Kaempferol 3-O-acetyl-glucoside; Kaempferol 3-O-galactoside; Kaempferol 3-O-

OH O galactoside 7-O-rhamnoside; Kaempferol 3-O-glucoside; Kaempferol 3-O-glucosyl- 88 77 66 55 44 33 22’’ 33’’ 44’’ 55’’ 66’’ rhamnosyl-galactoside; Kaempferol 3-O-sophoroside; Kaempferol 3-O-glucosyl- rhamnosyl-glucoside; Kaempferol 3-O-glucuronide; Kaempferol 3-O-rhamnoside;

Kaempferol 3-O-rhamnosyl-rhamnosyl-glucoside; Kaempferol 3-O-sophoroside 7-O- glucoside; Kaempferol 3-O-xylosyl-glucoside; Kaempferide. Quercetin*; Quercetin 3,4'-O-diglucoside; Quercetin 3-O-(6"-malonyl-glucoside); Quercetin 3-O-(6"-malonyl-glucoside) 7-O-glucoside; Quercetin 7,4'-O-diglucoside; Quercetin 3-O-(6''-acetyl-galactoside) 7-O-rhamnoside; 3,7-Dimethylquercetin; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ OH Quercetin 3-O-acetyl-rhamnoside; Quercetin 3-O-xylosyl-rutinoside; Quercetin 3-O-

OH galactoside; Quercetin 3-O-galactoside 7-O-rhamnoside; Quercetin 3-O-glucoside; Quercetin 3-O-glucosyl-rhamnosyl-galactoside; Quercetin 3-O-glucosyl-rhamnosyl- HO O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Quercetin*; glucoside; Quercetin 3-O-glucosyl-xyloside; Quercetin 3-O-glucuronide; Quercetin 3-

OH Isorhamnetin O-rhamnoside; Quercetin 4'-O-glucoside; Quercetin 3-O-rhamnosyl-galactoside; r = 0.67 OH O Quercetin 3-O-xylosyl-glucuronide; Quercetin 3-O-rhamnosyl-rhamnosyl-glucoside; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Quercetin 3-O-rutinoside; Quercetin 3-O-sophoroside; Quercetin 3-O-xyloside; Quercetin 3-O-arabinoside; Isorhamnetin; Isorhamnetin 3-O-glucoside;

Isorhamnetin 3-O-galactoside; Isorhamnetin 3-O-glucoside 7-O-rhamnoside; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Isorhamnetin 3-O-glucuronide; Isorhamnetin 3-O-rutinoside; Isorhamnetin 4'-O- glucoside; Isorhamnetin 7-O-rhamnoside; Rhamnetin. OH

8 7 6 5 4 3 2’ 3’ 4’OH 5’ 6’

HO O 8 7 6 5 4 3 2’ 3’ 4’OH 5’ 6’ Myricetin*; Myricetin 3-O-arabinoside; Myricetin 3-O-galactoside; Myricetin 3-O- 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Myricetin* OH glucoside; Myricetin 3-O-rhamnoside; Myricetin 3-O-rutinoside. r = 0.72 OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

8 7 6 5 4 3 2’ 3’ 4’OH 5’ 6’ OH 8 7 HO6 5 4 O3 2’ 3’ 4’ 5’ 6’

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ HO OH 6,8-dihydroxykaempferol*

OH O 88 77 66 55 44 33 22’ ’ 33’’ 44’’ 55’’ 66’’

8 7 6 5 4 3 2 ’ 3 ’ 4 ’ 5 ’ 6 ’

8 7 6 5 4 3 2’ 3’ 4’ O 5’ 6’ O O O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ 3-Methoxynobiletin* O O

O O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ 8 7 6 5 4 3 2 ’ 3 ’ 4 ’ 5 ’ 6 ’

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

8 7 6 5 4 3 2’ O3’ 4’ 5’ 6’ 3-Methoxysinensetin* ;5,3',4'-Trihydroxy-3-methoxy-6:7-methylenedioxyflavone 4'-

O O-glucuronide; 5,4'-Dihydroxy-3,3'-dimethoxy-6:7-methylenedioxyflavone 4'-O-

O O glucuronide; Patuletin 3-O-(2''-feruloylglucosyl)(1->6)-[apiosyl(1->2)]-glucoside; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Patuletin 3-O-glucosyl-(1->6)-[apiosyl(1->2)]-glucoside; Jaceidin 4'-O-glucuronide; O O Spinacetin 3-O-(2"-feruloylglucosyl)(1->6)-[apiosyl(1->2)]-glucoside; Spinacetin 3-O- O O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ (2"-p-coumaroylglucosyl)(1->6)-[apiosyl(1->2)]-glucoside; Spinacetin 3-O-glucosyl-(1- >6)-glucoside; Spinacetin 3-O-glucosyl-(1->6)-[apiosyl(1->2)]-glucoside.

1 Characterising structure based on the compound, with the smallest functional groups, that is reported in either database. For brevity and clarity, structures are drawn in a 2-dimensional plane. Coloured squares represent carbons on the flavan nucleus to which functional groups are attached. * Indicates characterising compound. r: pearson correlation coefficient, P < 0.01. Supplementary Table 2: Flavanol compounds reported in the United States Department of Agriculture (USDA) O and Phenol-Explorer (PE) databases OH Compounds Compounds Aglycone structure1 reported in USDA reported in PE OH

HO O (-)-epicatechin*; (-)-epicatechin 3-O-gallate; (+)- (-)-epicatechin*; (+)-catechin*. catechin*; (+)-catechin 3-O-gallate; (+)-catechin 3-O- OH r = 0.91 glucose. OH 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O OH (-)-epigallocatechin*; (-)-epigallocatechin*; (-)-epigallocatechin 3-O-gallate; (+)- (-)-epigallocatechin 3-gallate; (+)- OH gallocatechin*; (+)-gallocatechin 3-O-gallate. r = 1.00 gallocatechin*. OH 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

OH O HO

O OH

HO HO O Theaflavin*; Theaflavin-3,3'-digallate; Theaflavin*; Theaflavin 3,3'-O-digallate; Theaflavin 3'-O- OH Theaflavin-3-gallate; Theaflavin-3'-gallate. gallate; Theaflavin 3-O-gallate. OH r = 1.00 OH 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ 02 mers; Procyanidin dimer B1; Procyanidin dimer B2; Procyanidin dimer B3; Procyanidin dimer B4; Procyanidin dimer B5; Procyanidin dimer B7; Prodelphinidin dimer B3; r = 0.75 03 mers; Procyanidin trimer C1; Procyanidin trimer C2; Dimers; Trimmers; 4-6mers; 7-10mers; Procyanidin trimer EEC; Procyanidin trimer T2; Polymeric compounds Polymers; Thearubigins Prodelphinidin trimer C-GC-C; Prodelphinidin trimer GC- C-C; Prodelphinidin trimer GC-GC-C; 04-06 mers; 07-10 mers; Polymers (>10 mers); (-)-epicatechin-(2a- 7)(4a-8)-epicatechin 3-O-galactoside; Cinnamtannin A2.

1 Characterising structure based on the compound, with the smallest functional groups, that is reported in either database. For brevity and clarity, structures are drawn in a 2-dimensional plane. Coloured squares represent carbons on the flavan nucleus to which functional groups are attached. * Indicates characterising compound. r: pearson correlation coefficient, P < 0.01. Supplementary Table 3: Flavone compounds reported in the United States Department of Agriculture (USDA) O and Phenol-Explorer (PE) databases

O Compounds Compounds Aglycone structure1 reported in reported in PE USDA OH

HO O 7,4'-Dihydroxyflavone*

O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O 7,3',4'-Trihydroxyflavone*; Geraldone.

O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O

Chrysin* OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O Apigenin*; Apigenin 7-O-(6''-malonyl-apiosyl-glucoside); Apigenin 7-O-apiosyl-glucoside; r = 0.34 Apigenin* Apigenin 7-O-diglucuronide; Apigenin 7-O-glucoside; Apigenin 7-O-glucuronide; OH O Rhoifolin; Rhoifolin 4'-O-glucoside; Isorhoifolin. 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

OH OH Luteolin*; Luteolin 7-O-(2-apiosyl-6-malonyl)-glucoside;

HO O Luteolin 7-O-(2-apiosyl-glucoside); Luteolin 7-O-diglucuronide; Luteolin 7-O-glucoside; Luteolin 7-O-glucuronide; Luteolin 7-O-malonyl-glucoside; Luteolin* r = 0.40 Luteolin 7-O-rutinoside; Pebrellin; Diosmin; Chrysoeriol 7-O-glucoside; OH O Chrysoeriol 7-O-apiosyl-glucoside; Chrysoeriol 7-O-(6''-malonyl-glucoside); Chrysoeriol 7- 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ O-(6''-malonyl-apiosyl-glucoside); Neodiosmin.

HO O Baicalein* HO

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O Scutellarein*; Tetramethylscutellarein; Cirsimaritin; Apigenin 6-C-glucoside; HO Hispidulin. OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O 6-Hydroxyluteolin*; 6-Hydroxyluteolin 7-O-rhamnoside; Luteolin 6-C-glucoside; Nepetin; Cirsilineol; Sinensetin; Eupatorin; Jaceosidin. HO

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

O O

O O Gardenin B*; Apigenin 6,8-di-C-glucoside; Apigenin arabinoside-glucoside; Apigenin

O galactoside-arabinoside; Tangeretin. OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

O O

O O 5,6-Dihydroxy-7,8,3',4'-tetramethoxyflavone*; Nobiletin. HO OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

1 Characterising structure based on the compound, with the smallest functional groups, that is reported in either database. For brevity and clarity, structures are drawn in a 2-dimensional plane. Coloured squares represent carbons on the flavan nucleus to which functional groups are attached. * Indicates characterising compound. r: pearson correlation coefficient, P < 0.01. Supplementary Table 4: Flavanone compounds reported in the United States Department of Agriculture (USDA) O and Phenol-Explorer (PE) databases

O Compounds Compounds Aglycone structure1 reported in reported in PE USDA

HO O Pinocembrin

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O Naringenin; Naringenin 7-O-glucoside; Naringin; Naringin 4'-O-glucoside; Naringin 6'- Naringenin r = 0.99 malonate; Narirutin; Narirutin 4'-O-glucoside; Sakuranetin; Didymin; Poncirin. OH O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O

6-Prenylnaringenin*; 6-Geranylnaringenin.

OH O

8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

HO O 8-Prenylnaringenin*; Isoxanthohumol.

OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

OH OH

HO O Eriodictyol*; Eriodictyol*; Eriodictyol 7-O-glucoside; Eriocitrin; Neoeriocitrin; Hesperetin; r = 0.99 Hesperetin Hesperidin; Neohesperidin. OH O 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’

Supplementary Table 5: Anthocyanidin compounds reported in the United States Department of Agriculture HO O+ (USDA) and Phenol-Explorer (PE) databases

OH Compounds Compounds Aglycone structure1 reported in reported in PE USDA OH Pelargonidin*; Pelargonidin 3,5-O-diglucoside; Pelargonidin 3-O-sambubioside; HO O+ Pelargonidin 3-O-(6''-malonyl-glucoside); Pelargonidin 3-O-(6''-succinyl-glucoside);

OH Pelargonidin* Pelargonidin 3-O-arabinoside; Pelargonidin 3-O-galactoside; Pelargonidin 3-O-glucoside; r = 0.74 OH Pelargonidin 3-O-glucosyl-rutinoside; Pelargonidin 3-O-rutinoside; Pelargonidin 3-O- 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ sophoroside. Cyanidin*; Cyanidin 3,5-O-diglucoside; Cyanidin 3-O-(6''-acetyl-galactoside); Cyanidin 3- O-(6''-acetyl-glucoside); Cyanidin 3-O-(6''-caffeoyl-glucoside); Cyanidin 3-O-(6''-dioxalyl- OH glucoside); Cyanidin 3-O-galactoside; Cyanidin 3-O-(6''-malonyl-3''-glucosyl-glucoside) ; OH Cyanidin 3-O-xylosyl-rutinoside; Cyanidin 3-O-(6''-malonyl-glucoside); Cyanidin 3-O-(6''- HO O+ p-coumaroyl-glucoside); Cyanidin 3-O-(6''-succinyl-glucoside); Cyanidin 3-O-arabinoside; Cyanidin*; Cyanidin 3-O-glucosyl-rutinoside; Cyanidin 3-O-rutinoside; Cyanidin 3-O-glucoside; OH Peonidin r = 0.88 Cyanidin 3-O-sambubioside; Cyanidin 3-O-sambubiosyl 5-O-glucoside; OH 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Cyanidin 3-O-sophoroside; Cyanidin 3-O-xyloside; Peonidin; Peonidin 3-O-(6''-acetyl- galactoside); Peonidin 3-O-(6''-acetyl-glucoside); Peonidin 3-O-(6''-malonyl-glucoside); Peonidin 3-O-(6''-p-coumaroyl-glucoside); Peonidin 3-O-arabinoside; Peonidin 3-O- galactoside; Peonidin 3-O-glucoside; Peonidin 3-O-rutinoside. Delphinidin 3,5-O-diglucoside; Delphinidin 3-O-(6''-acetyl-galactoside); Delphinidin 3-O-(6''-acetyl-glucoside); Delphinidin 3-O-(6''-malonyl-glucoside);

OH Delphinidin 3-O-(6''-p-coumaroyl-glucoside); Delphinidin 3-O-sambubioside; Delphinidin

OH 3-O-feruloyl-glucoside; Delphinidin 3-O-galactoside; Delphinidin 3-O-glucoside; Delphinidin 3-O-glucosyl-glucoside; Delphinidin 3-O-rutinoside; Delphinidin 3-O- HO O+ Delphinidin*; OH xyloside; Delphinidin 3-O-arabinoside; Malvidin 3,5-O-diglucoside; Malvidin 3-O-(6''- Malvidin; OH acetyl-galactoside); Malvidin 3-O-(6''-acetyl-glucoside); Malvidin 3-O-(6''-caffeoyl- r = 0.84 Petunidin OH glucoside); Malvidin 3-O-(6''-p-coumaroyl-glucoside); Malvidin 3-O-arabinoside; 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’ Malvidin 3-O-galactoside; Malvidin 3-O-glucoside; Petunidin 3,5-O-diglucoside; Petunidin 3-O-(6''-acetyl-galactoside); Petunidin 3-O-(6''-acetyl-glucoside); Petunidin 3- O-(6''-p-coumaroyl-glucoside); Petunidin 3-O-arabinoside; Petunidin 3-O-galactoside; Petunidin 3-O-glucoside; Petunidin 3-O-rhamnoside; Petunidin 3-O-rutinoside.

HO O+ O

O OH

O Vitisin A*; Pigment A; Pinotin A. O OH

O OH OH

OH 8 7 6 5 4 3 2’ 3’ 4’ 5’ 6’