Antioxidant Properties of 3-Deoxyanthocyanidins And

Antioxidant properties of 3-deoxyanthocyanidins and polyphenolic extracts from Côte d’Ivoire’s red and white sorghums assessed by ORAC and in vitro LDL oxidisability tests Marie-Annette Carbonneau, Moctar Cisse, Nathalie Mora-Soumille, Sofiane Dairi, Maxence Rosa, Françoise Michel, Céline Lauret, Jean-Paul Cristol, Olivier Dangles

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Marie-Annette Carbonneau, Moctar Cisse, Nathalie Mora-Soumille, Sofiane Dairi, Maxence Rosa, et al.. Antioxidant properties of 3-deoxyanthocyanidins and polyphenolic extracts from Côte d’Ivoire’s red and white sorghums assessed by ORAC and in vitro LDL oxidisability tests. Food Chemistry, Elsevier, 2014, 145, pp.701-709. 10.1016/j.foodchem.2013.07.025. hal-02634650

HAL Id: hal-02634650 https://hal.inrae.fr/hal-02634650 Submitted on 27 May 2020

HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Version postprint Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript 3-deoxyanthocyanidins and polyphenolic extracts fromCôte d’Ivoire’s redand whitesorghums assessed 3Ds.Ti nqefaueicessterceia tblt at stability chemical their C-ring increases the feature in unique group This hydroxyl (3-DAs). a display ( not 3-position do they since (Tsuda, diseases unique chronic of prevention the 2012 in relevant be may that plants in these 2009 colours general, red In and sorghum. purple, ( blue, in the class to flavonoid contribute pigments major the are nins (‘‘dolo’’) hydroxybenzo beer local a of production beverages. and in- for non-fermented for porridge) and porridge), used (thin (thick often is food ‘‘tô’’ sorghum fant of Malted food). preparation (granulated the couscous is for grain sorghum used non-germinated countries, generally Africa, several West in In food Africa. staple in the notably is Sorghum world. the in crops rnos Michel Françoise iai E Vitamin oxidation lipoprotein density Low capacity absorption radical Oxygen polyphenols Sorghum luteolinidin apigeninidin, 3-Deoxyanthocyanidins, Keywords: http://dx.doi.org/10.1016/j.foodchem.2013.07.025 matter front see - 0308-8146/$ xrcsfo ôedIor’ e n ht ogusasse yORAC by assessed sorghums white and and red d’Ivoire’s Côte from extracts d c b a ai-net Carbonneau Marie-Annette polyphenolic and 3-deoxyanthocyanidins of properties Antioxidant .Introduction 1. Journal homepage: Food Chemistry Ve wk,Roe,&Wnsa 04 ohd,Mr,&Kondo, & Mori, Yoshida, 2004; Waniska, & Rooney, Awika, nvriyo vgo,IR,UR48 40 vgo,France Avignon, 84000 408, UMR INRA, Avignon, of University M 0 URPS,Uiest nttt fCiia eerh 4,A.DynGso iad 49 otele ee ,France 5, Cedex Montpellier 34093 Giraud, Gaston Doyen Av. 641, Research, Clinical of Institute University NUTRIPASS, 204 UMR NH,19 aosoko ôed’Ivoire Côte Yamoussoukro, 1093 INPHB, eateto iceity aerneHsia,CR 7,A.DynGso iad 49 otele ee ,France 5, Cedex Montpellier 34295 Giraud, Gaston Doyen Av. 371, CHRU Hospital, Lapeyronie Biochemistry, of Department ⇑ ogu otissgicn uniiso hnlcaislike acids phenolic of quantities significant contains Sorghum ogu bicolor Sorghum orsodn uhr e. 3 1799;fx 3 467542731. +33 fax: 411759892; +33 Tel.: author. Corresponding -aladdress: E-mail r Carbonneau, M.-A.(Auteur decorrespondance), Cisse, M.,Mora-Soumille, N.,Dairi, S.,Rosa, si ,adpsesatoiatadat-namtr properties anti-inflammatory and antioxidant possess and ), .Srhmatoyndn atoynnalcns are aglycones) (anthocyanin anthocyanidins Sorghum ). on définitive du du m on définitive nvitro in M., Michel, F.,Lauret, C., Cristol,J.-P., Dangles,O. (2014).Antioxidant properties of by ORAC and in vitro LDL oxidisability tests. Food Chemistry, 145, 701-709. DOI : i.1 Fig. ic [email protected] n yrxcnai cd.Mroe,anthocya- Moreover, acids. hydroxycinnamic and n hsaecle 3-deoxyanthocyanidins called are thus and )

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foodchem : : ver 10.1016/j.foodchem si on of theof on ma droxybenz amounts ino ity te (Et ether addi- and diethyl filtrate of the tion of min. evaporation 90 after 4 for collected at was solution precipitate kept the was through mixture bubbled The gently was NaCl) solid ae.Tecuepoutwsprfidb ounchromatography column by purified (SiO was product crude The rated. lcai)ad2 HPLC and or acid) grade (6-hydroxy-2,3,7,8-tetramethylchroman-2-carbox- ylic reagent either Trolox are grade. used chemicals from (Conches, Biovalley Other purchased from France). was were AAPH Germany). (HPLC) (Darmstadt, high-per- Merck France), chromatography for methanol Fallavier, liquid grade Quentin ultra-gradient formance and (Saint acid were Aldrich gallic reagent while Sigma Folin–Ciocalteu from 2N the obtained and (BHT) hydroxytoluene odrotie a isle ndymtao MO)(0mL) N (20 under equiv) (MeOH) (10 methanol MeONa with dry treated in and dissolved was obtained powder eiu a uie ycrmtgah nslc e (SiO gel silica on chromatography by purified was residue 6 nm. 468 rsue 0 Lo tA eeadd h rai ae was layer organic The room added. (3 at reduced were water days EtOAc under with 3 washed of concentration for mL 100 and stirred pressure, and filtration vigorously mL) was After (120 mL) temperature. (30 THF acid mmol), 27 acetic g, (5 3,4-dihydroxyacetophenone re vrNa over dried coun- the of interior the and Abidjan try, in markets several at d’Ivoire rxbnadhd eedsovdi itle tA 3 L and mL) 0 (30 to EtOAc cooled distilled in dissolved 4-acetoxy-2,6-dihy- were droxybenzaldehyde and 2,4-diacetoxy-6-hydroxybenzaldehyde M 1 with washings After added h. 5 was for equiv) refluxed (2 (2 was HCl anhydride mixture Acetic the mL). (50 and EtOAc in solved and mmol) 12 VVssetu yia fanthocyanins: of displayed typical detected peak spectrum sole The UV/Vis nm. 280 a at detection with [ DAD of purity The ec,respectively. Merck, 7 m VVs(H3ctaebuffer), citrate 3 (pH UV/Vis nm. 471 1,s H,59 1,s O) .3(,3,COCH 3H, (s, 2.53 1OH), s, (1H, 5.99 OH), s, (1H, hnn sawieaopospwe:yed 90%; yield, powder: amorphous white a as phenone 1,dd, (1H, et oafr ue[ pure afford to lent) esprtda ht mrhu odradietfid yield, identified: and powder diacetylated amorphous white and 65%; a mono- could as of separated 2,4-diacetoxy-6-hydroxybenzaldehyde mixture be a Only, afford to compounds. v/v) 95:5 EtOAc, – tA,11,0.47; 1:1), EtOAc, J iiagl(odEu atigsC8 atcesz 40–63 size reversed-phase particle on C18, eluted cartridges was Elut solution (Bond The gel mL). (2 silica HCl dissolved M was 0.01 condensation, in incomplete from 4 resulting at [ materials overnight containing kept (wet powder crude then 1–3 the HCl, pH ration, M to 1 with acidified paper) carefully pH was solution the temperature, .5(H d, (1H, 8.35 inadprfiain 62%; purification: and tion ..Ceia ytei 3 synthesis Chemical 2.2. .,H 1.9, = t R 2,4-Diacetoxy-6-hydroxybenzaldehyde ’57Tiyrxflvlu hoie=apigeninidin = chloride 4’,5,7-Trihydroxyflavylium itr fatvtdzn odr( ,7 mmol), 76 g, (5 powder zinc activated of mixture A ogu bicolor Sorghum 2 then 42min, 14.2 HxEOc : /)t iecmon 3,4-dihydroxyaceto- compound give to v/v) 1:1 cHex/EtOAc, , R f nu ce/tA,73,0.47; 7:3), (cHex/EtOAc, 5 1 J 0 L n ae (2 water and mL) 100 ,66 1,d, (1H, 6.63 ), 2mo)o -yrxaeohnn n itr of mixture a and 4-hydroxyacetophenone of mmol) (2 aldehyde -M (DMSO-d H-NMR ie n lae ormv ers CuCl debris. remove to cleaned and mixed . n . z H Hz, 8.3 and 2.0 = sc .GsosHl(eeae yato f9%H 98% of action by (generated HCl Gaseous °C. J .2013.07.025 ri 2 .,H 8.7, = k pt publis SO 1 N max a aeul hce yrvrepaeHPLC- reverse-phase by checked carefully was ] ,N 4 0 7 1 ,,-rhdoyezleye(.5g, (1.85 2,4,6-Trihydroxybenzaldehyde . 7 nm. 276 : dmtyaioyiie(. qi)wr dis- were equiv) (0.2 -dimethylaminopyridine n ocnrtdudrrdcdpesr.The pressure. reduced under concentrated and -M (CDCl H-NMR 0 (L.) dclrfloeci eefo lrc and Aldrich from were -dichlorofluorescein 1 3 .Oealyedfrcnesto,deacetyla- condensation, for yield Overall ]. ,81 2,d, (2H, 8.15 ), J hed Moench 0 ,4 2 .,H 1.9, = ) fe rcptto nEOc h red the EtOAc, in precipitation After O). 0 L,didoe Na over dried mL), 100 0 -dihydroxyacetophenone 6

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3 grains (nBuOH/HOAc/H 3 ,23 3,s c,23 3,s Ac). s, (3H, 2.32 Ac), s, (3H, 2.39 ), ), 1 0 L,teognclyrwas layer organic the mL), 100 M (CDCl NMR H d 1 .7(H d, (1H, 7.67 J ,NC n eiulstarting residual and NaCl ], .,H 8.8, = were d and .4(H d, (1H, 9.04 e 2 20 M 22400 = fe 0mna room at min 90 After . ucae rmCôte from purchased J 2 4-acetoxy-2 0 . z H Hz, 8.3 = ,H t 3 R 2 2 ), J SO ,321,0.83. 3:2:1), O, .Atrevapo- After °C. 6 .,H 2.0, = 92min, 29.2 [ 0 d 3 ,70 2,d, (2H, 7.07 ), 1 4 ;HPLC-DAD ); ]. .7(H d, (1H, 6.67 2 n evapo- and butylated , J Equimolar 1 .,H 8.7, = x R l cm f -chloro- 2 5 ;Agi- m; 2 2 ,6-dihy- cHex/ , 0 SO 0 (cHex/ ,6.19 ), ,7.55 ), 1 k 4 max on 4 at ), Version postprint Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript 3-deoxyanthocyanidins and polyphenolic extracts fromCôte d’Ivoire’s redand whitesorghums assessed fcetfrteetato fttlatoynn.TeEWH The anthocyanins. total of extraction the for efficient PCpr e odr vrl il,71%; yield, [ overall powder: gel, red silica HPLC-pure reversed-phase and on reacidification purification deacetylation, After [ dihydroxyacetophenone. for as procedure are u tlati rpiae h EWH The 3000 triplicate. in Rotavapor at least a at centrifuged out on carried concentrated and then 40 temperature was at supernatant room The at min. 10 h 3 for 8 nm. 481 rcdr novdteadto f5 LEO n 0m H mL 50 and EtOH mL 50 of extraction addition The study. the this involved in employed procedure was flour whole the and NJ) .8(H d, (1H, 8.08 cdfidb ctcai p .)t 0go hl ort obtain to flour whole of g (EWH 10 extract to ethanol/water 2.6) acidic (pH an acid acetic by acidified a are u o eoigtemr yrpoi compounds hydrophobic more the removing (CHCl for out carried was k mixed) M (DMSO-d NMR (C J n D xdto tests. oxidation LDL and (C oi-icle egn codn oamdfidprocedure modified a to according ( reagent Folin-Ciocalteu xrse nmlio fgli cdeuvln e ir (mmol litre per equivalent acid gallic L of GAE millimol in expressed ipae VVssetu yia fanthocyanins: of typical detected spectrum peak sole UV/Vis The a nm. displayed 280 at detection [ with of HPLC-DAD phase purity The 0.77; 3:2:1), . LH mL 1.4 dwsue o PCadseta nlss hn LEWH mL 2 Then, analyses. spectral and HPLC for used was od eesdpaeclm ihope 0 P1 (250 RP-18 a on 100 (DAD) Lichrospher detector array column diode a phase with HPLC reversed by out carried were iue C n 100 and PCs diluted (C wk ta. 2004 al., et (Awika extraction methanol HCl) (1% fied 61(C 96.1 (C 160.0 d, (1H, 7.06 d 84,Dtce A rmt,Fac)t ban1 Lo naque- an of (EWH compounds mL polyphenolic 11 of obtain extract to ous France) Brumath, SA, Dutscher 3000 5804R, at centrifuged and texed ae o C for lated unicto a bandb eotn h absorbance L the mmol 0.7–3.0 standard a reporting as range: used acid by gallic of (concentration curve calibration obtained the on France). measured XL was Colmar, Uvicon a SAS, using Quantification Instruments nm 765 (BIO-TEK at spectrophotometer measured were values at incubated Absorbance were Samples mL. 2 of 40 volume final a obtain to added, CHCl mL 8 to added quantification 271.0606. found, 271.0601; ...Dtriaino hnlcontent phenol of Determination 2.3.2. 2.3.1. and extraction polyphenol preparation, sample flour Whole 2.3. Journal homepage: Food Chemistry Ve aehue 2001 Waterhouse, max .,H 8.8, = 6 1 10 9 02MTFA), M /0.2 0 (C 149.7 ), o 0mn esrmnswr efre ntriplicate. in performed were Measurements min. 30 for °C 3 ape fsrhmgan(olce ndfeetmresand markets different on (collected grain sorghum of Samples h hnlcaon nEWH in amount phenolic The eaainadqatfiaino h EWH the of quantification and Separation r ,180(C 118.0 ), Carbonneau, M.-A.(Auteur decorrespondance), Cisse, M.,Mora-Soumille, N.,Dairi, S.,Rosa, ,105(C 110.5 ), si 0 ,4 8 m VVs(H3ctaebuffer), citrate 3 (pH UV/Vis nm. 485 oafia oueo 5m.Teetato rcdr was procedure extraction The mL. 25 of volume final a to °C 3 Preparation on définitive du du m on définitive 0 57Ttayrxflvlu hoie=luteolinidin = chloride ,5,7-Tetrahydroxyflavylium 1 hs)adwssseaial ple ro oteORAC the to prior applied systematically was and phase) were ). 8 9 3 M., Michel, F.,Lauret, C., Cristol,J.-P., Dangles,O. (2014).Antioxidant properties of 2 1 ;HRMS-ESI, ); ,172(C 157.2 ), 0 by ORAC and in vitro LDL oxidisability tests. Food Chemistry, 145, 701-709. DOI : eepae notbsad300 and tubes into placed were O -M (DMSO-d H-NMR ,H 15 H J 5 J 0 4 .,H 8.7, = 11 odrdi Ds il Ge il n. Clifton, Inc., Mills (Glen Mill’ ‘Disk a in powdered ,69 1,s H s, (1H, 6.97 ), 3 5 .,H 8.8, = ,139(C 133.9 ), d 6 ,131(C 103.1 ), 0 O ,161(C 116.1 ), 02MTFA), M /0.2 7. (C 172.3 4 fwoeflu n apeextraction sample and flour whole of +

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foodchem R oxidation E Vitamin .6±0.02 ± 0.46 i VtE ( E) (Vit : : ver 10.1016/j.foodchem si on of theof on ma l 2 * * * * * * * o L mol hnwiesrhmad3Ds t fetvns so h order 3- the its and of quercetin is oxidation LDL effectiveness of Its inhibitors efficient potent 3-DAs. the more of and (LDL as sorghum used up came white was extract than test sorghum physiological red more the oxidisability), a when However, ghum. xrcspsesasgicn rerdclsaegn activity radical-scavenging in (expressed free concentration phenolic given significant a For sorghum test). the a (ORAC that show possess study luteolinidin our extracts 3-DAs, of results synthesised The to antiox- apigeninidin. their and comparison determine in to order activities in idant d’Ivoire, Côte from flour whole extractabl A L GAE oeraitcsrcue oesivliglpd n proteins (loosely and assay. ORAC lipids the involving to preferred models be activity, should antioxidant structured their realistic for screened more are PCs When rutin. coside eitrsigt vlaeteatoiatatvt fpoorly of sor- red activity in present antioxidant flour. be whole could the ghum that PCs evaluate bound) (strongly to extractable interesting quantification escape be thus and residues ( extraction the amounts in significant because content remain underestimated often polyphenolic is foods the plant that of demonstrated have investigations htnu,L,Tvn,A,L eci,C,Jcb,D . r,Ngi . ei . tal. et F., Levi, E., Negri, Jr., R., D. Jacobs, C., Vecchia, La A., Tavani, L., Chatenoud, ato,E,Fue,G,Crona,M . art . ihl . one,L,e al. et L., Monnier, F., Michel, C., Lauret, A., M. Carbonneau, G., Fouret, E., Cartron, for sorghum red of Potentiality (2011). S. Collin, & V., Jerkovic, M., C-glycosyl- (2009). Bröhan, M. O. Andersen, & K., Kalberg, T., Fossen, S., antioxidant, Rayyan, Comparative O., (2009). Bjoroy, A. Faraj, & D., J. Browning, L., Yang, M., J. Awika, cardiovascular atherosclerotic against protect grains Whole (2003). W. J. Anderson, .Conclusion 4. ato,E,Crona,M . ort . ecms . ée,C .(01.Specific (2001). L. C. Léger, & B., Descomps, G., Fouret, A., M. Carbonneau, E., Cartron, wk,J . ony .W,&Wnsa .D 20) nhcaisfo black from Anthocyanins (2004). D. R. Waniska, & W., L. Rooney, M., J. Awika, References 1 .I ol also could It 2013). Carcea, & Maiani, Azzini, Turfani, Durazzo, min nti td,w aeivsiae h opsto feasily of composition the investigated have we study, this In oyhnl npat a ecasfida aiyextractable easily as classified be can plants in Polyphenols 37 77 (2012). wine-description of types three comparing two study of a in plasma in characteristics 278–287 opud:LLpoeto gis xdto n eraei the in decrease and (2003). oxidation against production. 64 Products, lysophosphatidylcholine protection proinflammatory LDL compounds: 59 activity. Chemistry, antioxidant Food and high Agricultural with beers stilbenoid-enriched producing anthocyanidins bicolor antiproliferative disease. antioxidant sorghum 1021–1035 , 24–28 , 1 ) 1 nu ,wiesrhmcudee emr oetta e sor- red than potent more be even could sorghum white ), varieties. ) O bound) Whole Red-wine rceig fteNtiinScey 62 Society, Nutrition the of Proceedings mtyae eiaie fgli cdi humans. in acid gallic of derivatives -methylated e . sc and . oyhnlccmonso e n ht sorghum white and red of compounds polyphenolic 480–486 , 1. 25.5 ± 115.0 t .2013.07.025 ri VitE activity 48±7.0 ± 94.8 0.5 ± 45.5 2.5 ± 72.5 4.2 ± 85.7 11.2 ± 41.7 03±0.5 ± 60.3 10±8083±0.8 ± 8.3 8.0 ± 31.0 hi nixdn properties. antioxidant their pt publis 2+ . ri oditk n acrrisk. cancer and intake food grain (min) mdae D peroxidation. LDL -mediated and synthesized W – LWT rpol xrcal srnl on) Recent bound). (strongly extractable poorly or eeca ogtr feto iisbtnto antioxidant on not but lipids on effect long-term beneficial hs Iezm nuigptnilo ogu ( sorghum of potential inducing enzyme II phase . fcfey eiaie n te aua phenolic natural other and derivatives caffeoyl of * * * * * . * * odSineadTcnlg,42 Technology, and Science Food hed

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l * * * o L mol odCeity 90 Chemistry, Food 135–142 , . 1 nentoa ora fCancer, of Journal International min 1 ) . 1041–1046 , reRdclResearch, Radical Free htceity 70 Phytochemistry, ora fNatural of Journal 293–301 , 7. 25.0 ± 172.3 2. 13.6 ± 225.5 t 0. 9.0 ± 101.4 lag 87±12.8 ± 58.7 98±12.8 ± 79.8 11.2 ± 93.6 93±7.2 ± 39.3 90±4.2 ± 49.0 (min) . ora of Journal Sorghum O . l -gly- * * * mol * * * * * , Version postprint Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript Manuscrit d’auteur / Author manuscript 3-deoxyanthocyanidins and polyphenolic extracts fromCôte d’Ivoire’s redand whitesorghums assessed age,O,&E aj,H 19) ytei f3mtoy n 3-( and 3-methoxy- of Synthesis (1994). H. Hajji, El & O., Dangles, sioo . a,A,Ysiua . mkr,Y,Ysia . aao . ta.(2012). al. et T., Hatano, T., Yoshida, Y., Amakura, M., Yoshimura, A., Tai, H., Ishimoto, od-oao,M,Nro . nin .(96.Ttlasgmn of assignment Total (1996). B. Ancian, & M., Narco, M., Kouda-Bonafos, from Africans South black of diet staple flavonoids, the by of change promotion The Health (2005). (2005). C. A. Isaacson, Peroxidative Jenner, (2001). & J. J., P. Rafter, O’Brien, B., & Halliwell, S., T. Chan, Y., M. Moridani, G., Galati, 3 (1997). R. Brouillard, & P., Figueiredo, O., Dangles, H., lignans Hajji, Phenols, El (2013). M. Carcea, & G., Maiani, E., Azzini, V., Turfani, A., Durazzo, chemistry, phenolics: and Dietary mechanisms chemical (2009). phenols: plant N. of activity Antioxidant M. (2012). O. Clifford, Dangles, & I., Jaganath, A., Crozier, olad . roé .C . asan . orsy .(04.Mdln of Modeling (2004). M. Kouressy, & M., Vaksmann, S., C. P. Traoré, A., Folliard, Journal homepage: Food Chemistry Ve pyranosyloxy) 370–382 Antioxidative qeu ouin yrgnbniga eno oorvariation. in colour of properties mean their a 80 of as Acta, Chimica bonding investigation Hydrogen and solution. aqueous synthesis ions: nosyloxy)flavylium sesdb nOA assay. ORAC 395–399 an by assessed effects? indirect esophagus. the or direct sorghum phenols: other not? and or Antioxidant tocotrienols, tocopherols, conjugation. and oxidation glutathione metabolism 89 Research, flours. chestnut sweet and legume 140 of properties antioxidant and solution. aqueous in 1595–1610 anthocyanins of reactivity the biological health. on effects and bioavailability sorghum M hmclsit fantrlatoyndn pgnndn sn two- using apigeninidin, anthocyanidin, natural a of shifts chemical NMR r Carbonneau, M.-A.(Auteur decorrespondance), Cisse, M.,Mora-Soumille, N.,Dairi, S.,Rosa, si on définitive du du m on définitive 666–671 , M., Michel, F.,Lauret, C., Cristol,J.-P., Dangles,O. (2014).Antioxidant properties of by ORAC and in vitro LDL oxidisability tests. Food Chemistry, 145, 701-709. DOI : . . response to significance. . 59–70 , az cr)i h as fteeiei fsunu acnm of carcinoma squanous of epidemic the of cause the is (corn) maize . of flavylium properties eia yohss 64 Hypotheses, Medical 398–413 , pgnnadnaringenin and apigenin opooeid hehl–yeblcapproach. threshold–hyperbolic a photoperiod: to .

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