Journal of Food Engineering 128 (2014) 167173

Contents lists available at !ien!e"ire!t

Journal of Food Engineering

#ournal$o%e&age'((()elsevier)!o%*lo!ate*#foodeng

Caractersticas De Adsorcin / Desorcin Y La Separacin De Los Antocianos Y Polifenoles De Los Arndanos Utilizando Resinas Adsorbentes Macroporosas
+i%ot$, J) -uran. /%andee& 0) and$u. 1$eng 2i. C$er,l 3) 3o!4. 5ei$ua 5) 6ang. 2i(ei 7u
Food !ien!e and 8u%an 9utrition "e&art%ent. :nstitute of Food and /gri!ultural !ien!es. ;niversit, of Florida. 7ainesville. F2 32611. ;nited tates

arti!le info
/rti!le $istor,' 3e!eived 21 /ugust 2013 3e!eived in revised for% 4 "e!e%ber 2013 /!!e&ted 24 "e!e%ber 2013 /vailable online 4 Januar, 2014

abstra!t
2os ar<ndanos !ontienen fito>u?%i!os antio@idantes. !o%o las anto!ianinas . flavonoles , &ro!ianidinas . !on %u!$os benefi!ios &ara la salud ) En el &resente estudio . los fito>u?%i!os de ar<ndanos se e@tra#eron %ediante e!ograf?a asistida e@tra!!i=n de agua !aliente , se !on!entraron !on resinas de adsor!i=n /%berlite ) Ensa,os de adsor!i=n est<ti!a de%ostraron >ue la resina FAB66 ten?a una %a,or !a&a!idad de adsor!i=n , desor!i=n de rela!i=n >ue las resinas B/"78A , B/"4 ) B/"761 , B/"1180 %ostraron la !a&a!idad de desor!i=n %<s ba#a , la rela!i=n ) Ensa,os de adsor!i=n , de isoter%as 0ineti! revelado >ue FAB66 ten?a la %<s alta efi!ien!ia de adsor!i=n , re>uiere un tie%&o %<s !orto &ara al!anCar el e>uilibrio de adsor!i=n ) /dsor!i=n din<%i!a en FAB 66 resina en una !olu%na de vidrio de%ostrado >ue las anto!ianinas en el e@tra!to de ar<ndanos agua !o%enCaron a ro%&er des&uDs de 16 volE%enes de le!$o de e@tra!to se !arg= ) ;n desor!i=n !o%&leta se !onsigui= usando 3 volE%enes de le!$o de FG H E+8 I /nol ) Cien gra%os de ar<ndanos fres!os dio 0.80 g e@tra!to !on!entrado de ar<ndanos ) /CE!ares no se dete!taron en el e@tra!to ) 2013 Elsevier 2td) /ll rig$ts reserved)

Palabras clave: /r<ndanos 2as anto!ianinas 3esinas /dsor!i=n "esor!i=n

11 ) :ntrodu!!i=n /r<ndanos fres!os se sabe >ue tienen %a,or !a&a!iIdad antio@idante >ue otras frutas (5u et al) . 2004 ) ) 2os fito>u?%i!os de los ar<ndanos son re&ortados a redu!ir el !olesterol en la sangre ( Arior et al. 200F ) ) 6 &revenir el !<n!er , la ateros!lerosis (/da%s et al. 2010 J ) ) 5u et al. 2010 ) ) 2a investiga!i=n sugiere >ue los fito>u?%i!os e@tra?dos de los ar<ndanos eran %<s efi!a!es >ue las frutas enteras en I ing &revenir el au%ento de &eso !or&oral ( Arior et al) . 2008 ) ) 2os ar<ndanos !ontienen F.F6 g de aCE!ar &or 100 g de fruta fres!a ( ; "/ . 2012 ) ) Cer!a de 8)3 H , el 3G H de la &obla!i=n de los EE);;) son diabDti!os o &re IdiabDti!os (C"C. 2011 ) ) Este gru&o de !onsu%idores , &Ebli!o en general &uede benefi!iarse de un &rodu!to !on &o!o o ningEn !ontenido de aCE!ar) Aor lo tanto . $a, una de%anda de suI I gar libre de ar<ndanos fito>u?%i!os , !on!entrada en for%a de un su&le%ento dietDti!o &ara &resu%ir la ingesta de antio@idantes , la &reven!i=n de enfer%edades ) +e!nolog?a de adsor!i=n de la resina se est< e@&lorando &ara !on!entrar &olifenoles , &ara eli%inar los aCE!ares ( 0a%%erer et al . 200G J ) ) oto et al . 2011 ) ) 3esinas sintDti!as &er%iten la adsor!i=n de los &olifenoles de solu!i=n a!uosa a travDs de a&ila%iento de uni=n , aro%<ti!o $idr=fobo ) Ellos desorben fito>u?%i!os en disolventes org<ni!os. tales !o%o %etanol o etanol ) "ebido a >ue los aCE!ares no intera!tEan !on resinas . >ue se &ueden eli%inar f<!il%ente &or elu!i=n en agua ) El ultrasonido fue investigado &ara au%entar la efi!ien!ia de e@tra!!i=n) 2os &olifenoles atra&ados en la %atriC de la &lanta fueron &uestos en libertad de %anera efe!tiva &or el ultrasonido en anteriores /utor &ara !orres&onden!ia) +el ' K1 (3G2) 3F2 1FF1 @210 J ) fa@' ) K1 (3G2) 3F2 F467 E I%ail' 27uLufl)edu (2) 7u ) ) 0260I8774 * M I see front %atter 2013 Elsevier 2td) +odos los dere!$os reservados ) $tt&'**d@)doi)org*10)1016*#)#foodeng)2013)12)02F

estudios ( C$e%at et al) . 2011 ) ) En el &resente estudio . la alta !a&a!idad de e@tra!I!i=n de ultrasonidos de &oten!ia se a!o&l= !on la !a&a!idad de !on!entra!i=n de la adsor!i=n de la resina &ara &rodu!ir e@tra!tos !on!entrados fito>u?%i!os de ar<ndanos) 2 ) Nateriales , %Dtodos 2)1 ) Arodu!tos Ou?%i!os //A8 ( 2.20 I aCotis ( 2 I a%idino&ro&ano ) ) era un &rodu!to de 5a4o C$e%i!als :n!) ( -ell(ood . 3: ) ) +rolo@ ( <!ido G.7.8 I tetra%etilben!eno t$,l!$ro%an I 2 I !arbo@?li!o 6 I $idro@i I 2 ) , !ianidina 3 I rutin=sido se ad>uirieron de ig%a I /ldri!$ ( t) 2ouis. NP ) ) 9or%as de los 3 IP- Iglu!=sidos de &elargonidina . !ianidina . &eonidina . delfinidina . &etunidina , %alvidin (seis nor%a anto!ianina %i@ta . grado 8A2C) . se !o%&raron de &olifenoles 2aboratories ( andnes. 9oruega)) 3ea!tivo de Folin ICio!alteu . <!ido !lorogDni!o , otros &rodu!tos >u?%i!os eran &rodu!tos de Fis$er !ientifi! ( Aittsburg . A/ ) ) 3esinas /%berlite ( B/"761 . B/"4 . B/"1180 . B/"78A , FAB66 ) fueron &rodu!to de 3o$% 8ass ( A$iladel&$ia . A/)) Aro&iedades >u?%i!as , f?si!as de estas resinas se resu%en en la +abla 1 ) 2)2 ) AreI trata%iento de las resinas 3esinas se sus&endieron en agua &ara e@&andir las &erlas antes de su envasado en una !olu%na de vidrio ( 2 :" ' 22 3G0 %% ) ) El etanol ( 140 %l . FG H ) se us= &ara lavar la !olu%na !on un !audal de 400 %l * $ ) Colu%na se lav= !on agua $asta >ue el elu,ente era

168

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173

+able 1 Aro&iedades >u?%i!as , f?si!as de las resinas /%berlite resins B/"4 B/"78A B/"761 C$e%i!al %atri@ urfa!e 2 area (% *g) 7G0 G00 200 Aarti!le siCe (%%) 0)31)2 0)6 0)7 Aore envelo&e (Q) 100 4G0 600

"esor&tion ratio

Sd "H R Cd TC0 CeUSi

"esor&tion !a&a!it,

100

T3U

B/"1180 FAB66

Crosslin4ed aro%ati! &ol,%er Crosslin4ed aro%ati! &ol,%er Crosslin4ed for%o&$enoli! &ol,%er Crosslin4ed aro%ati! &ol,%er Crosslin4ed aro%ati! &ol,%er

Sd >d R Cd CdSd T1 NU5 T4U

H 3e!over,

G00 700

0)21)F 0)600)7G

400 2002G0

3 R C0S0

100H

TGU

($ere " is t$e desor&tion ratio (H). >d is t$e desor&tion !a&a!it, (%g*g dr, resin). and 3 is t$e re!over, (H) after desor&tion is !o%I&lete) C d is t$e !on!entration of ant$o!,anins or total &$enoli!s in t$e desor&tion solution (%g*2)) Sd is t$e volu%e of t$e desor&tion solution (%2)) C0. Ce. N. 5. and Si are t$e sa%e as above) 2)G) /dsor&tion 4ineti!s AreItreated resin (1 g) (as %i@ed (it$ 2G %2 of blueberr, (ater e@tra!t in a flas4 and &la!ed in a (ater bat$ s$a4er (4G r&%) at roo% te%&erature) /n ali>uot of su&ernatant (1 %l) (as obtained ever, 30 %in for t$e first 6 $ and t$en ever, 60 %in fro% 6 to 12 $) /dsor&tion 4ineti!s (as evaluated using t$e &seudo first and se!ond order %odels) Aseudo first order %odel

!lear) +$e resin (as t$en eluted (it$ 140 %2 of 4H 8Cl follo(ed b, distilled (ater until &8 of t$e eluent be!a%e neutral) +$e !olu%n (as t$en (as$ed (it$ 140 %2 of GH 9aP8. follo(ed b, distilled (ater until t$e eluent rea!$ed a &8 of 7)0) a%&les of t$e &reItreaIted resins (ere (eig$ed into alu%inu% dis$es and 4e&t in an oven at 60 2C for 24 $) 5eig$t loss (as !al!ulated as %oisture !ontent) 2)3) E@tra!tion of &$,to!$e%i!als fro% blueberries FroCen sout$ern $ig$ bus$ blueberries (160 g) (ere %i@ed (it$ 400 %2 of $ot (ater (F0 2C. a!idified (it$ 0)GH v*v a!eti! a!id) and blended for 1 %in in a blender) / &o(er ultrasound &robe (as &la!ed into t$e blueberr, %as$ and t$e %i@ture (as soni!ated (20 48C) at 100H a%&litude for G %in) +$e e@tra!tion %i@ture (as filtered t$roug$ !$eese !lot$ to se&arate (ater e@tra!t and blueberr, residue) +$e residue (as reIe@tra!ted (it$ an additional 400 %2 of a!idified (ater b, using ultrasound) +$e (ater e@tra!ts (ere !o%bined and filtered t$roug$ 5$at%an 9o) 4 filter &a&ers) 2)4) tati! adsor&tion*desor&tion testing AreItreated $,drated resin (1 g) and 2G %2 of blueberr, (ater e@tra!t (ere added to 2G0 %2 Erlen%e,er flas4s (it$ sto&&ers) Flas4s (ere 4e&t for s$a4ing in a (ater bat$ s$a4er ( tovall 2ife !ien!es :n!)J 7reensboro. 9C) at a rate of 4G r&%) /dsor&tion (as !ondu!ted at roo% te%&erature (2G 2C) for 24 $) For stati! desor&tion testing. t$e &$,to!$e%i!alIladen resins (ere (as$ed (it$ 2G %2 distilled (ater) /fter (ater (as$. G0 %2 of FGH et$anol (as added in t$e flas4s) +$e flas4s (ere 4e&t in a (ater bat$ s$a4er at 4G r&% for 24 $ at roo% te%&erature) /dsor&tion and desor&Ition ratios and !a&a!ities (ere !al!ulated using t$e follo(ing e>uations' /dsor&tion ratio

lnT>e >t U R ln >e 4f t

Aseudo se!ond order %odel

T6U

1 R 4 s> e V
2

>

>

T7U

($ere 4f is t$e rate !onstant of t$e &seudoIfirstIorderI%odel and 4 s is t$e rate !onstant of t$e &seudoIse!ondIorderI%odel. > t (%g*g) is t$e a%ount of ant$o!,anins or total &$enoli!s adsorbed at ti%e t and > e is t$e adsor&tion !a&a!it, at e>uilibriu%) 2)6) /dsor&tion isot$er%s and t$er%od,na%i!s FAB66 resin (as sele!ted for adsor&tion isot$er%s and t$er%oI d,na%i!s testing) 8,drated resin (1 g) (as added to 2G %2 blueIberr, (ater e@tra!ts of different !on!entrations) /dsor&tion (as !ondu!ted at t$ree different te%&eratures (2G. 3G. or 4G 2C) in a s$a4ing (ater bat$ at 4G r&%) +$e e>uilibriu% adsor&tion isoIt$er%s for total &$enoli!s and total ant$o!,anins (ere deter%ined using 2ang%uir and Freundli!$ e>uations) 2ang%uir e>uation

>e R

>%Ce 02 V C e T8U

/H
T

TC0 CeU UR C0 TSiU

e

1 T
U

($ere >% (%g*g) is t$e %a@i%u% a%ount of adsor&tion. 0 2 is t$e affinit, !onstant in 2ang%uir %odel ($i!$ !an be !al!ulated fro% t$e slo&e and inter!e&t of t$e linear &lot of Ce*>e versus Ce. res&e!tivel,) Freundli!$ e>uation

/dsor&tion !a&a!it,
>
e

>e R 0F C1eWn 2 T
U

TFU

C
0

T1 NU5

($ere / is t$e adsor&tion ratio (H) and > e is t$e adsor&tion !a&a!it, (%g*g dr, resin) at e>uilibriu%) C0 and Ce is t$e initial and e>uilibIriu% !on!entrations of ant$o!,anins or total &$enoli!s in t$e blueIberr, e@tra!t solutions (%g*2). res&e!tivel,) N is t$e %oisture !ontent of t$e resin ((*(. H) ($ereas 5 is t$e initial (eig$t of t$e resin being used (g)) Si is t$e volu%e (%2) of blueberr, e@tra!t used)

($ere b, &otting log >e vs log Ce. !onstant 0F and an e@&onent of 1*n !an be !al!ulated) 2)7) ",na%i! adsor&tion*desor&tion testing

/ glass !olu%n (it$ a fritted dis4 (:)") 2. 1F 400 mm) was loaded with FPX66 resin with a resin bed volume of 30 mL. Blue-berry water e tra!t was loaded into this !olumn usin" a flow rate

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173

16F

of 2. G or 10 -S*$. res&e!tivel,) +$e adsorbateIladen !olu%n (as t$en (as$ed (it$ (ater (1G0 %2) to re%ove sugars and ot$er !o%&ounds t$at did not absorb on t$e resin) A$,to!$e%i!als (ere desorbed using FGH et$anol at a flo( rate 2. 4. or 6 -S*$. res&e!Itivel,) Eluent (as !olle!ted and anal,Ced for total ant$o!,anin and &$enoli! !ontent)

gas 11 2*%in. dr,ing te%&erature 300 2C. and !a&illar, of 4000 S. allo(ing !o%&ounds to be dete!ted in bot$ &ositive and negative %ode in t$e sa%e run) +$e full s!an %ass s&e!tra of t$e ant$o!,aI nins (ere re!orded fro% %*C 3G0 to 6G0) /uto N (as !ondu!ted (it$ 100H !o%&ound stabilit, and 100H tra& drive level) Aure !o%I &ounds of !$lorogeni! a!id. rutin. %,ri!etin. >uer!etin. and 4ae%&ferol (ere used as e@ternal standards to >uantif, !$lorogenIi! a!id and flavonols) /nt$o!,anin glu!oside %i@ture (as used as an e@ternal standard for t$e >uantifi!ation of ant$o!,anins) "ata (as anal,Ced using C$e%station soft(are (Sersion -) 01)03. /giIlent +e!$nologies. Aalo /lto. C/)) -lueberr, &$,to!$e%i!als (ere identified on t$e basis of full s!an and &rodu!t ion %ass s&e!tra. ;S*S: s&e!tra on diode arra, dete!tor. and !o%&arison (it$ &ubIlis$ed &a&ers (C$o et al). 2004J 5u and Arior. 200G)) ugar anal,sis (as !ondu!ted using a 3este4 ultra a%ino !olIu%n (G l%. 2G0 4)6 %%)) /!etonitrile' (ater (6G'3G v*v) (as used as t$e %obile &$ase at a !onstant flo( rate of 1)0 %2*%in) +$e !olu%n te%&erature (as %aintained at 30 2C and G l2 of sa%I&le (as in#e!ted) Calibration !urves (ere !onstru!ted using &ure standards of glu!ose and fru!tose) 2)12) tatisti!al anal,ses "ata (ere e@&ressed as %ean X standard deviation) PneI(a, anal,ses of varian!e (it$ +u4e,0ra%er 8 " !o%&arison of %eans (ere &erfor%ed using JNA soft(are (Sersion 8)0. / :nstiItute :n!). Car,. 9C)) / differen!e of & 6 0)0G (as !onsidered as signifi!ant)
2

2)8) FolinCio!alteu assa, +otal &$enoli! !ontent (as deter%ined b, t$e FolinCio!alteu assa, (2ee et al). 200G)) -lueberr, e@tra!ts (ere %i@ed (it$ diluted FolinCio!alteu reagent and 1GH sodiu% !arbonate) /bsorban!e at 76G n% (as %easured on a AEC+3/%a@ 1F0 %i!ro&late reader (Nole!ular "evi!es. unn,vale. C/) after 30 %in of in!ubation at roo% te%&erature) 7alli! a!id (as used to generate a standard !urve) 3esults of total &$enoli! !ontent for blueberries (ere e@I&ressed as %illigra% galli! a!id e>uivalent &er gra% of froCen fres$ blueberr, sa%&les (%g 7/E*g)) 2)F) +otal ant$o!,anin !ontent +otal ant$o!,anin !ontent (as %easured b, using a &8 differIential assa,) /bsorban!e at G20 and 700 n% (as %easured on a 2ife !ien!e ;S*Sis s&e!tro&$oto%eter ("; 730. -e!4%an Coulter. Fullerton. C/) after 1G %in of in!ubation at roo% te%&erature) /bsorban!e (/) (as !al!ulated using (/G20/700)&8 1)0 (/G20 /700)&8 4)G) +otal ant$o!,anin !ontent (%g C,7*g) (as !al!ulated using (/ 44F)0 80 1000)*(2F.740 1) for blueberr, and (as e@&ressed as %illigra% !,anidin 3Iglu!oside e>uivalent &er gra% of froCen fres$ blueberr, (%g C,7*g)) 2)10) P@,gen radi!al absorban!e !a&a!it, (P3/C)

3) 3esults and dis!ussion 3)1) tati! adsor&tion and desor&tion +$e P3/C assa, for blueberr, sa%&les (as !ondu!ted on a &e!tra BN 7e%ini &late reader (Nole!ular "evi!es. unn,vale. C/)) -riefl,. G0 l2 of standard and sa%&les (ere added to t$e desI ignated (ells of a F6I(ell bla!4 &late) +$is (as follo(ed b, t$e addition of 100 l2 of fluores!ein (20 nN)) +$e %i@ture (as in!uIbated at 37 2C for 7 %in before t$e addition of G0 l2 of //A8) FluoIres!en!e (as %onitored using 48G n% e@!itation and G30 n% e%issions at 1 %in intervals for 40 %in) +rolo@ (as used to generIate a standard !urve) +$e antio@idant !a&a!ities of e@tra!ts (ere e@&ressed as %i!ro%oles of +rolo@ e>uivalents (+E) &er gra% (l%ol of +E*g)) /dsor&tion and desor&tion be$aviors of ant$o!,anins on resins are de&i!ted in Fig) 1(/1 and /2)) /%berlite resin FAB66 and B/"1180 $ad t$e $ig$est adsor&tion ratio of FF)8H and F6)7H. res&e!tivel, (Fig) 1/1)) B/"761 s$o(ed t$e lo(est at 7F)8H) B/"78A s$o(ed t$e $ig$est adsor&tion !a&a!it, (2G)8 %g*g) (it$ FAB66 and B/"1180 follo(ing at 24)1 and 23)F %g*g. res&e!tivel,) B/"4 $ad t$e lo(est adsor&tion !a&a!it, at 17)F %g*g ($en !o%I&ared to t$e ot$er resins des&ite t$at B/"4 $ad t$e $ig$est surfa!e area of 700 % *g (+able 1)) 8o(ever. t$e lo( adsor&tion !a&a!it, of B/"4 %a, be e@&lained b, its ver, s%all &ore envelo&e siCe of 100 Q) Arevious resear!$ suggested t$at t$e surfa!e area in !o%biInation (it$ &ore siCe (ere t$e deter%ining fa!tors in &redi!ting t$e adsor&tion !a&a!it, (Bu et al). 1FFF)) :n desor&tion tests. FAB66 and B/"761 $ad a $ig$er desor&tion ratio (121)1H and 11F)FH) and greater re!over, t$an t$e ot$er resins (Fig) 1/2)) FAB66 and B/"761 $ave relativel, large &arti!le siCes at 0)7G %% and 0)70 %%. res&e!tivel,) 3esins (it$ larger &arti!le siCes tend to $ave $ig$er %ass e@!$ange rates and allo( %ore %aterial to be transferred to and fro% t$e resin. t$ereb, in!reasing t$e desor&tion ratio and re!over,) +$e adsor&tion and desor&tion be$aviors of total &$enoli!s on resins are des!ribed in Fig) 1(-1 and -2)) B/"761 $ad t$e $ig$est adsor&tion !a&a!it, and ratio of G3)4 %g*g and 88)6H. res&e!tivel,) B/"78A s$o(ed t$e lo(est adsor&tion ratio at 70)6H. ($ereas FAB66 and B/"4 (ere in bet(een (Fig) 1-1)) :n !ontrast to a $ig$ adsor&tion ratio. B/"761 $ad t$e lo(est desor&tion ratio of 21)0H and a re!over, of onl, 16)GH) B/"761 is a &olar &$enol for%aldeI$,de &ol,%er (di&ole %o%ent W 1)80). ($ereas t$e ot$er adsorIbents are %ade of st,renedivin,lbenCene. a $,dro&$obi! &ol,aro%ati! &ol,%er (di&ole %o%ent W 0)30)) +$erefore B/" 761 resin $as $ig$er adsor&tion affinit, to(ards &$enoli! !o%I&ounds (it$ $ig$ &olarit, t$an $,dro&$obi! resins ( ilva et al).
2

2)11) 8A2C anal,ses of &$,to!$e%i!als and sugars /n /gilent 1200 8A2C s,ste% !onsisting of an autosa%&ler. a binar, &u%&. a !olu%n !o%&art%ent. a diode arra, dete!tor and a refra!tive inde@ dete!tor (/gilent +e!$nologies. Aalo /lto. C/) (as interfa!ed to a 8C+ ion tra& %ass s&e!tro%eter (-ru4er "alItoni!s. -illeri!a. N/)) a%&les (ere !entrifuged at 13.300 r&% for 10 %in and 10 l2 of su&ernatant (as in#e!ted for &$,to!$e%i!al anal,sis) / 1orba@ -IC18 !olu%n (2G0 %% 4)6 %%. G l% &artiI!le siCe. /gilent +e!$nologies. Aalo /lto. C/) (as used for t$e se&Iaration) +$e binar, %obile &$ase !onsisted of (/) for%i! a!id' (ater (G'FG v*v) and (-) %et$anol) For t$e anal,sis of flavonols. !$lorogeni! a!id derivatives and ant$o!,anins. a 70I%in gradient (as ada&ted fro% a &ublis$ed &a&er (C$o et al). 2004)) +$e gradiIent is des!ribed as follo(s' 0 %inI GH -. 2 %inIGH -. 10 %inI20H -. 1G %inI20H -. 30 %inI2GH -. 3G %inI2GH -. G0 %inI33H -. GG %inI40H -. 60 %inI60H -. 6G %inI70H -. 70 %inIGH - iso!rati!J folIlo(ed b, G %in of reIe>uilibration of t$e !olu%n before t$e ne@t run) +$e dete!tion (avelengt$ (as G20 n% for ant$o!,anins. and 360 n% for !$lorogeni! a!id and flavonols) Ele!tros&ra, ioniCation in alternating %ode (as &erfor%ed using nebuliCer 30 &si. dr,ing

170

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173

Fig) 1) (/1) tati! adsor&tion !a&a!it, and ratio. and (/2) re!over, and desor&tion ratio of total ant$o!,anins) (-1) tati! adsor&tion !a&a!it, and ratio. and (-2) re!over, and desor&tion ratio of total &$enoli!s) 3esults are %ean of t$ree deter%inations) "ifferent u&&erI!ase letters indi!ate signifi!ant differen!es of solid bars) "ifferent lo(erI!ase letters indi!ate signifi!ant differen!es of lined bars)

40

A s!rpti!" capacity (mg/g)

FPX 66 XAD 4 XAD 7HP

+able 2 Aseudo first and se!ond order rate !onstants of resins !al!ulated on t$e basis of total &$enoli!s and total ant$o!,anins) 3esins Aseudo first order +otal ant$o!,anins 0F >e Correlation !oeffi!ient (3 ) FAB66 B/"4 B/"78A FAB66 B/"4 B/"78A FAB66 B/"4 B/"78A FAB66 B/"4 B/"78A 0)004 0)003 0)004 0)00G 0)003 0)004 0)032 0)003 0)018 4 1)02 10 4 4)G0 10 6)61 10
4 2

30

20

+otal &$enoli!s

1)1F 1)G0 1)21 1)4F 1)77 1)G1 1)37 2)07 2)01 68)0 G6)G G8)8

0)F88 0)FGF 0)FG4 0)F34 0)F7G 0)F7F 0)FF6 0)F87 0)FF7 0)FF3 0)FFF 1)000

#0

Aseudo se!ond order +otal ant$o!,anins

0 0 200 400 600 $00

+otal &$enoli!s

%ime (mi")
70

A s!rpti!" capacity (mg/g)

60 '0 40 30 20

&

2007)) / signifi!ant a%ount of &$enoli! !o%&ounds in blueberr, e@tra!t %a, $ave been adsorbed irreversibl, on B/"761 resin and attributed to t$e e@tre%el, lo( re!over, and desor&tion ratio of &$enoli! !o%&ounds) FAB66 (as t$e %ost effi!ient resin in desor&tion (it$ re!over, of 82)GH and a desor&tion ratio of 114)FH (Fig) 1-2)) tati! tests indi!ated t$at FAB66. B/"78A and B/"4 (ere !onI sistentl, %ore effi!ient at adsor&tion and desor&tion t$an ot$er t(o resins. $en!e t$e, (ere !$osen for furt$er 4ineti! tests) 3)2) /dsor&tion 4ineti!s

#0 0 200 400 600 $00

%ime (mi")
Fig) 2) /dsor&tion 0ineti!s of total ant$o!,anins (/) and total &$enoli!s (-) fro% blueberr, (ater e@tra!t) 3esults are %ean of t$ree deter%inations)

#he adsor$tion %ineti!s of antho!yanins and total $henoli!s on FPX66& X'()*P and X'(4 resins is shown in Fi". +. FPX 66 and X'()*P rea!hed e,uilibrium at a$$ro imately 4 h and 6 h& res$e!-tively& whi!h was faster than X'(4 -about . h). 't e,uilibrium&

FPX 66 had a hi"her adsor$tion !a$a!ity than X'()*P or X'(4

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173 +able 3 2ang%uir and Freundli!$ e>uation !onstants of total ant$o!,anins and total &$enoli!s on /%berlite FAB66 resin)
0(07 0(06

171

2 &e ,!l-me/. ' &e ,!l-me/. #0 &e ,!l-me/.

A"t.!cya"i" )!"te"t (mg/+)

+e%&erature (2C) +otal ant$o!,anins 2G 3G 4G +otal &$enoli!s 2G 3G 4G

2ang%uir e>uation
14'8Ce
1'18VCe

32

Freundli!$ e>uation
0'02G >e R 0'0F1Ce 0'244 >e R 0'176Ce 0'086

32

0(0' 0(04 0(03 0(02 0(0# 0(00 0 ' #0 #' 20 2'

>e R >e R >e R >e R >e R >e R

0)FF7 0)FF8 0)FFG 0)F22 0)F22 0)F64

>e R 0'4GFCe >e R 0'G06Ce

0)142 0)767 0)888 0)F42 0)882 0)883

14'4Ce
0'731VC e

13'GCe 0'386VCe 10'7Ce 0'011VCe F'76Ce

0'010VC e

>e R 0'11GCe
0'617 0'784 0'8GF

16'8Ce 0'014VCe

>e R 0'G2FCe

,!l-me /l-te (m+)

#($ #(6 #(4 #(2 4

A
A"t.!cya"i" )!"te"t (mg/+)

'

&

2 &e ,!l-me/. 4 &e ,!l-me/. 6 &e ,!l-me/.

)e/*e

#(0 0($ 0(6 0(4 0(2 0(0 0 ' #0 #' 20 2' 30

2' )
3' )
!

! !

4' )

)e (mg/+)
3' 30 2'

20

40

60

$0

#00

#20

#40

#60

#$0

200

,!l-me /l-te (m+)

Fig) 4) ",na%i! adsor&tion (/) and desor&tion (-) !urves of total ant$o!,anins on /%berlite FAB66 resin at different flo( rates) 3esults are %ean of t(o deter%inations)

&

)e/*e

20 #' #0 ' 0 #00 200 300 400 '00

B/"78A resins rea!$ed e>uilibriu%) FAB66 $ad a $ig$er adsor&Ition !a&a!it, t$an B/"78A) /t t$e end of 7 $ B/"4 %at!$ed t$e adsor&tion !a&a!it, of FAB66) 0ineti! data using &seudo first and se!ond order %odels are de&i!ted in +able 2) i%ilar to total ant$oI !,anins. t$e &seudo se!ond order %odel a&&eared to be better t$an &seudo first order in des!ribing t$e adsor&tion 4ineti!s of total &$enoli!s fro% blueberr, (ater e@tra!ts on resins) 3)3) /dsor&tion isot$er%s and t$er%od,na%i!s of ant$o!,anins on FAB66 resin +$e total ant$o!,anins and &$enoli!s data for adsor&tion (as regressed a!!ording to t$e 2ang%uir and Freundli!$ isot$er%s e>uations) E>uation !onstants and !orrelation !oeffi!ients are listed in +able 3) +$e 2ang%uir and Freundli!$ isot$er%s are t$e %ost !o%%on %odels for e@&loring adsor&tion e>uilibriu% data) +$e Freundli!$ %odel assu%es t$at t$e surfa!e of t$e resin is $etI erogeneous in nature t$at is !$ara!teriCed b, sor&tion sites at difI ferent energies) :t des!ribes t$e adsor&tion be$avior of a %ono%ole!ular la,er as (ell as a %ultiI%ole!ular la,er) +$e 2angI%uir %odel des!ribes a %onola,er adsor&tion (it$ energeti!all, identi!al sor&tion sites as (ell as (it$out %utual intera!tions beIt(een t$e adsorbed %ole!ules ("uran et al). 2011)) +$e !orrelation !oeffi!ients in +able 3 de&i!t t$at t$e 2ang%uir %odel (as a better fit for t$e data) 3esults based on total ant$o!,anins s$o(ed t$at t$e %a@i%u% adsor&tion !a&a!it, (>%) re%ains !onsistent. i%&l,Iing t$at te%&erature did not signifi!antl, affe!t t$e adsor&tion !a&a!it,) 8o(ever. t$e 02 values de!reases as te%&erature inI!reases. suggesting adsor&tion of ant$o!,anins (as de!reased as

)e (mg/+)
Fig) 3) /dsor&tion :sot$er%s based on 2ang%uir e>uation of total ant$o!,anins (/) and total &$enoli!s (-) on /%berlite FAB66 resin fro% blueberr, (ater e@tra!t) 3esults are %ean of t$ree deter%inations)

(Fig) 2/)) 3egression of 4ineti! data using &seudo first order %odel rendered straig$t lines bet(een log (>e>t) and ti%e) +$e !orrelaItion !oeffi!ients lie bet(een 0)FG4 and 0)F88 (+able 2)) +$e &seudo first order %odel des!ribes t$e initial stages of t$e adsor&tion &roI!ess) +$e &seudo se!ond order %odel is %ore useful to &redi!t and des!ribe t$e entire adsor&tion &ro!ess) +$e &seudo se!ond order %odel a&&eared to be better t$an &seudo first order in des!ribing t$e adsor&tion 4ineti!s of ant$o!,anins fro% blueberr, (ater e@Itra!t on resins) i%ilar observations (ere %ade in &revious studies using /%berlite resins on different !o%&ounds (/bdulla$ et al). 200F)) /dsor&tion !a&a!it, of total &$enoli!s on FAB66 and B/"78A in!reased >ui!4l, (it$in t$e first 3 $. ($ereas a gradual in!rease (as observed on B/"4 (Fig) 2-)) /t 4 $ bot$ t$e FAB66 and

172

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173

+able 4 Content of ant$o!,anins. flavonols. !$lorogeni! a!id. and sugars in froCen fres$ blueberries and t$e !on!entrated blueberr, e@tra!t) Co%&ounds FroCen fres$ blueberries (%g*g berries) 0)37X 0)02 0)04X 0)00 0)12X 0)07 0)23X 0)01 0)04X 0)00 0)04X 0)00 0)08X 0)00 0)74X 0)01 0)04X 0)00 0)24X 0)00 1)F4X 0)03 0)02X 0)00 0)01X 0)00 0)01X 0)00 0)01X 0)00 6F)F7X 0)4G 6G)84X 1)3F 3)77X 0)12 68)3X 0)7 Con!entrated blueberr, e@tra!t (%g*g e@tra!t) 38)8 X 1)6 3)76 X 0)18 1F)4 X 0)1 21)1 X 0)1 3)4G X 0)1F 3)6F X 0)21 8)F4 X 0)1F G2)2 X 1)G 3)3F X 0)16 21)2 X 0)2 17G)F X 2)4 1)4G X 0)10 0)26 X 0)01 0)1F X 0)01 0)44 X 0)0F 9ot dete!ted 9ot dete!ted 21G X 2)13 7660 X 1)1

t$an 3 -S of et$anol) -e!ause of t$e s$ortest ti%e used for desor&I tion. $ig$est flo( rate (6 -S*$) (as !$osen) 3)G) A$,to!$e%i!al and sugar !o%&osition of e@tra!ts Contents of ant$o!,anins. flavonols. !$lorogeni! a!id. and sugIars in froCen fres$ blueberries or !on!entrated blueberr, e@tra!t are s$o(n in +able 4) 8ot (ater e@tra!t of blueberries !ontained fru!tose and glu!ose) ugar (as not dete!ted in !on!entrated e@Itra!ts using 8A2C anal,sis) +$e ant$o!,anins !ontent in t$e e@tra!t (as 17)6H ((*() !o%&ared (it$ 0)1FH ((*() in fres$ blueberries) +$e !on!entration of !$lorogeni! a!id and flavonols in t$e e@tra!t (as also in!reased b, over 20 folds !o%&ared (it$ fres$ berries) +$e ,ield of !on!entrated blueberr, e@tra!t (as 0)80 g &er 100 g fres$ berries) +$e re!over, rate of total &$enoli!s (as 4G)6H) +$e lo( re!over, of total &$enoli!s (as li4el, due to uns&e!ifi! nature of FolinCio!alteu assa,) For e@a%&le. as!orbi! a!id is !ounted as &$enoli! ($en using Folin Cio!alteu assa,. $o(ever. as!orbi! a!id is not absorbed on resins) +$e re!over, rate of total ant$o!,anins (as 72)GH. ($i!$ (as !o%&arable to a &revious stud, (Jia and 2u. 2008))

/nt$o!,anins Aeonidin 3Igala!toside C,anidin 3Iglu!oside Aeonidin 3Iarabinoside Aetunidin 3Igala!toside C,anidin 3Iarabinoside Aeonidin 3 gala!toside Aetunidin 3Iarabinoside Nalvidin 3Igala!toside Nalvidin 3Iglu!oside Nalvidin 3Iarabinoside +otal ant$o!,anins C$lorogeni! a!id and flavonols C$lorogeni! a!id N,ri!etin 3Ir$a%noside Ouer!etin 3Iglu!oside N,ri!etin 3Iglu!oside ugars Fru!tose (%g*g) 7lu!ose (%g*g) Pt$ers +otal &$enoli! !ontent (%g 7/E*g) P3/C (l%o2 +E*g)

4) Con!lusions /%berlite FAB66 resin (as t$e %ost suitable resin for t$e re!over, of ant$o!,anins and flavonoids fro% blueberr, (ater e@Itra!t) +$is (as attributed to its $ig$ adsor&tion and desor&tion !a&a!it, to(ards t$ese !o%&ounds) 3esin adsor&tion resulted in a !on!entrated blueberr, e@tra!t t$at !ontained 17)6H ((*() ant$o!,anins (it$ no dete!table sugars) +$is e@tra!t !ould &otenItiall, find a&&li!ation as a natural !olorant. dietar, su&&le%ent. antio@idant ingredient for fun!tional foods. and*or as a ra( %ateIrial in t$e !os%eti! and &$ar%a!euti!al industr, &re&arations) /!4no(ledge%ents +$is resear!$ is su&&orted in &art b, a 7rant fro% Florida "e&art%ent of /gri!ulture and Consu%er ervi!es. and traug$n Far%s at 5aldo Florida) 3eferen!es
/bdulla$. N)/). C$iang. 2). 9adee%. N). 200F) Co%&arative evaluation of adsor&tion 4ineti!s and isot$er%s of a natural &rodu!t re%oval b, /%berlite &ol,%eri! adsorbents) C$e%) Eng) J) 146 (3). 370376) /da%s. 2) ). A$ung. ). 6ee. 9). eera%. 9)A). 2i. 2). C$en. ). 2010) -lueberr, &$,to!$e%i!als in$ibit gro(t$ and %etastati! &otential of N"/IN-I231 breast !an!er !ells t$roug$ %odulation of t$e &$os&$atid,linositol 3I4inase &at$(a,) Can!er 3es) 70 (F). 3GF4360G) C"C. 2011) 9ational diabetes fa!t s$eet. 2011) Centers for disease !ontrol and &revention) Y$tt&'**((()!d!)gov*diabetes*&ubs*&df*ndfsZ2011)&df[ (a!!essed 07)0F)13)) C$e%at. F). 1ill e. 8). 0$an. N)0). 2011) /&&li!ations of ultrasound in food te!$nolog,' &ro!essing. &reservation and e@tra!tion) ;ltrason) ono!$e%) 18 (4). 81383G) C$o. N)J). 8o(ard. 2)3). Arior. 3)2). Clar4. J)3). 2004) Flavonoid gl,!osides and antio@idant !a&a!it, of various bla!4berr,. blueberr, and red gra&e genot,&es deter%ined b, $ig$I&erfor%an!e li>uid !$ro%atogra&$,*%ass s&e!tro%etr,) J) !i) Food /gri!) 84 (13). 17711782) "uran. C). PCdes. "). 7undogdu. /). entur4. 8)-). 2011) 0ineti!s and isot$er% anal,sis of basi! d,es adsor&tion onto al%ond s$ell (Arunus dul!is) as a lo( !ost adsorbent) J) C$e%) Eng) "ata G6 (G). 21362147) Jia. 7). 2u. B). 2008) Enri!$%ent and &urifi!ation of %ade!assoside and asiati!oside fro% Centella asiati!a e@tra!ts (it$ %a!ro&orous resins) J) C$ro%atogr) / 11F3 (12). 136141) 0a%%erer. "). 7a#dos 0l#usuri!. J). Carle. 3). !$ieber. /). 200G) 3e!over, of ant$o!,anins fro% gra&e &o%a!e e@tra!ts (Sitis vinifera 2) !v) Cabernet Nitos) using a &ol,%eri! adsorber resin) Eur) Food 3es) +e!$nol) 220 (3I4). 431437)

"ata are %ean X standard deviation for t$ree deter%inations)

te%&erature rose) "egradation of t$e $eat sensitive ant$o!,anins at $ig$er te%&eratures %a, e@&lain t$ese results) +$e 2ang%uir adsor&tion isot$er%s on FAB66 at 2G. 3G. and 4G 2C are s$o(n in Fig) 3) i%ilar to t$e isot$er% data on ant$o!,anins. t$e 2ang%uir e>uaI tion fitted t$e data ver, (ell (+able 3) for total &$enoli!s as (ell) +$e %a@i%u% adsor&tion !a&a!it, (>%) of total &$enoli!s and t$e 02 values (ere not affe!ted b, an in!rease in te%&erature e@!e&t at 4G 2C. ($ere bot$ >% and 02 in!reased) For bot$ ant$o!,anins and total &$enoli!s. FAB66 resin $ad t$e $ig$est adsor&tion effi!ien!, at lo(est te%&eraIture (2G 2C) and t$erefore. (as !$osen for d,na%i! testing) 3)4) ",na%i! adsor&tion*desor&tion on FAB66 resin 5$en blueberr, (ater e@tra!t (as loaded onto a FAB66 filled !olu%n. no ant$o!,anins (ere dete!ted in t$e eluent in t$e beginIning (Fig) 4/)) /fter %ore e@tra!t (as loaded. t$e resin in t$e !olIu%n slo(l, rea!$ed adsor&tion saturation) /nt$o!,anins started to brea4t$roug$ and a&&eared in t$e eluent) -rea4t$roug$ volu%e is defined as t$e volu%e of e@tra!t loaded on t$e !olu%n ($en t$e !on!entration of ant$o!,anins in t$e eluent is GH of t$at in (ater e@tra!t) /t a flo( rate of 10 -S*$ and G -S*$. t$e brea4t$roug$ volI u%es (ere 8 -S and 16 -S. res&e!tivel,) /t a flo( rate of 2 -S*$. brea4t$roug$ &oint (as not rea!$ed even after 23 -S of e@tra!t (as loaded on t$e !olu%n) +$e adsor&tion ratios of ant$o!,anins (ere F8)2H. 8F)3H. or 82)2H. res&e!tivel,. using a flo( rate of 2. G. or 10 -S*$) i%ilar results (ere re&orted in an earlier stud, t$at investigated t$e adsor&tion of l,!o&ene on resins (2iu et al). 2010)) +$e !onta!t ti%e bet(een ant$o!,anins and resin be!a%e s$orter ($en t$e flo( rate (as in!reased) $orter !onta!t ti%e subseI>uentl, led to an in!o%&lete adsor&tion (Na et al). 200F)) 3esults suggested t$at G -S*$ (as a suitable flo( rate as it allo(ed for %a@i%u% adsor&tion of &$enoli! !o%&ounds in t$e s$ortest a%ount of ti%e) Et$anol (FGH. v*v) (as used to desorb &ol,&$enols fro% !olu%n using a flo( rate of 2. 4. or 6 -S*$ (Fig) 4-)) 3egardless of flo( rate. a !o%&lete desor&tion of ant$o!,anins (as a!$ieved (it$ less

Lee& /.& (urst& 0.1.& 1rolstad& 0.2.& +003. (etermination of total monomeri! antho!yanin $i"ment !ontent of fruit 4ui!es& bevera"es& natural !olorants& and wines by the $* differential method5

!ollaborative study. /. '6'7 8nt. .. -3)& 9+6:;9+)..

+)J) -uran et al) * Journal of Food Engineering 128 (2014) 167173 2iu. 6). 2iu. J). C$en. B). 2iu. 6). "i. "). 2010) Are&arative se&aration and &urifi!ation of l,!o&ene fro% to%ato s4ins e@tra!ts b, %a!ro&orous adsor&tion resins) Food C$e%) 123 (4). 10271034) Na. C). +ao. 7). Jian+ang. 2ou. 1). 5ang. 8). 7u. B). 8u. 2). 6in. N). 200F) Are&arative se&aration and &urifi!ation of rosavin in 3$odiola rosea b, %a!ro&orous adsor&tion resins) e&) Aurif) +e!$nol) 6F (1). 2228) Arior. 3)2). 5u. B). 7u. 2). 8ager. +)J). 8ager. /). 8o(ard. 2)3). 2008) 5$ole berries versus berr, ant$o!,anins' intera!tions (it$ dietar, fat levels in t$e CG7-2*6J %ouse %odel of obesit,) J) /gri!) Food C$e%) G6 (3). 6476G3) Arior. 3)2). 5u. B). 7u. 2). 8ager. +). 8ager. /). 5il4es. ). 8o(ard. 2). 200F) Aurified berr, ant$o!,anins but not ($ole berries nor%aliCe li&id &ara%eters in %i!e fed an obesogeni! $ig$ fat diet) Nol) 9utr) Food 3es) G3 (11). 14061418) ilva. E)N). Ao%&eub. ")3). 2arondelle. 6). 3ogeC. 8). 2007) P&ti%isation of t$e adsor&tion of &ol,&$enols fro% :nga edulis leaves on %a!ro&orous resins using an e@&eri%ental design %et$odolog,) e&) Aurif) +e!$nol) G3. 274280) oto. N)2). Conde. E). Noure. /). "o%?ngueC. 8). Aara#=. J)C). 2011) 3e!over,. !on!entration and &urifi!ation of &$enoli! !o%&ounds b, adsor&tion' a revie() J) Food Eng) 10G (1). 127)

173

;nited tates "e&art%ent of /gri!ulture (; "/). /gri!ultural 3esear!$ ervi!e) 2012) ; "/ 9ational 9utrient "atabase for tandard 3eferen!e. 3elease 2G) Y$tt&'**ndb)nal)usda)gov*ndb*foods*s$o(*2184[ (a!!essed 07)10)13)) 5u. B). Arior. 3)2). 200G) ,ste%ati! identifi!ation and !$ara!teriCation of ant$o!,anins b, 8A2CE :N *N in !o%%on foods in t$e ;nited tates' fruits and berries) J) /gri!) Food C$e%) G3 (7). 2G8F2GFF) 5u. B). -ee!$er. 7)3). 8olden. J)N). 8a,to(itC. ")-). 7eb$ardt. )E). Arior. 3)2). 2004) 2i&o&$ili! and $,dro&$ili! antio@idant !a&a!ities of !o%%on foods in t$e ;nited tates) J) /gri!) Food C$e%) G2 (12). 40264037) 5u. B). 0ang. J). Bie. C). -urris. 3). Ferguson. N)E). -adger. +)N). 9agara#an. ). 2010) "ietar, blueberries attenuate at$eros!lerosis in a&oli&o&rotein EIdefi!ient %i!e b, u&regulating antio@idant enC,%e e@&ression) J) 9utr) 140 (F). 16281632) Bu. 1). 1$ang. O). C$en. J). 5ang. 2). /nderson. 7)0). 1FFF) /dsor&tion of na&$t$alene derivatives on $,&er!rosslin4ed &ol,%eri! adsorbents) C$e%os&$ere 38 (F). 20032011)