1. Introduction. 2. Material and methods. 40 th World Congress of Vine and Wine

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1 BIO We of Conferenes 9, 013 (17) 40 th World Congress of Vine nd Wine DOI:.1/ioonf/ Impt of different wood hip speies (ok, i nd herry) on evolution of individul nthoynins, hromti hrteristis nd ntioxidnt pity in model wine solutions António M. Jordão 1,, Virigini Lozno 2, An C. Correi 1, nd Mrí L. González-SnJosé 2 1 Instituto Politénio de Viseu (CI&DETS), Esol Superior Agrári, Estrd de Nels, Rnhdos, Viseu, Portugl 2 Universidd de Burgos, Fultd de Cienis, Deprtmento de Biotenologi e Cieni de los Alimentos, Plz Misel Bñuelos s/n, Burgos, Espñ Astrt. The im of present work ws to investigte the impt of different ok (Q. l, Q. rour nd Q. pyreni), i nd herry wood hips on evolution of individul nthoynin ontent, hromti hrteristis nd ntioxidnt pity y the use of model wine solutions. Aording to the results otined, model wine solutions ontining i nd espeilly herry wood extrts showed more evident hnges of individul nthoynin omposition, espeilly due to the formtion of lrge numer of new diret ondenstion nthoynins, thn model wines with ok extrts. These results were ompnied lso y higher olor degrdtion nd lower ntioxidnt potentil of solutions ontining the different wood hip extrt speies, ompred with solutions ontining only nthoynin lone. This reserh ontriutes to etter knowledge out the olor evolution of red wines when they re ging in ontt with new lterntive wood speies, espeilly i nd herry. 1. Introdution During red wine ging in ontt with ok wood, phenoli ompounds, minly nthoynins, undergo severl hnges tht my led to olor loss or stiliztion. Previous studied showed tht the origin or vriety of the ok together with the speifi prties of eh oopery, in ddition to the ge of the rrels nd the wine ging time in ontt with ok wood, ply key role in the formtion of new pigments whih ould improve hromti hrteristi of wines [1 3]. Despite the dvnes mde in the evolution of red wine olor nd omposition during wine ging in ontt with different ok wood speies [4 6], there is sre knowledge out the potentil impt on nthoynin, hromti hrteristis nd ntioxidnt pity evolution when red wines re ging in ontt with other non-ok wood speies. This is n importnt topi euse the high demnd of ok wood produts hs n eologil impt on hrvesting of ok trees in forest where the replement of trees is not gurnteed. Thus, the use of potentil lterntive woods, suh s i nd herry, my e n interesting option for potentil use in red wine ging proess. The im of present work ws to investigte the impt of ok (Frenh, Amerin nd Ierin speies), i nd herry wood hips on evolution of individul nthoynin ontent, hromti hrteristis nd ntioxidnt pity y the use of model wine solutions. e-mil: ntoniojordo@esv.ipv.pt 2. Mteril nd methods 2.1. Wood hip smples The wood hip smples used were: i (Ai pseudoroini) hips purhsed y SAI ompny (Predes, Portugl), herry (Prunus vium) Frenh nd Amerin ok (Querus petre nd Querus l, respetively) hips purhsed y AEB Bioquími ompny (Viseu, Portugl), nd Ierin ok hips from Portugl (Querus pyreni) purhsed y J.M. Gonçlves ompny (Plçoulo, Portugl), with medium tosting ( min t C), prtile size of 8 mm nd sumitted to nturl drying Model wine solutions Aliquots of red model wine solution (12% ethnol, djusted to ph 3. with trtri-trtrte uffer nd ontining grpe isolted nthoynins) ws dded with different wood hip onentrted extrts (finl onentrtion orresponding to 4 g wood hips/l wine) from ok, i nd herry speies otined fter 1 nd dys of extrtion. After mixing, the different solutions were stored during dys under ontrolled temperture (round 14 C) nd drkness onditions. All ssys were mde in duplite Methods By the use of HPLC-DAD, the individul nthoynin ontent evolution ws nlyzed followed the methodology desried y Pérez nd González-Snjosé [7], while hromti hrteristis evolution (olor intensity) ws studied y spetrophotometri methodologies [8], nd The Authors, pulished y EDP Sienes. This is n Open Aess rtile distriuted under the terms of the Cretive Commons Attriution Liense 4.0 (

2 BIO We of Conferenes 9, 013 (17) 40 th World Congress of Vine nd Wine DOI:.1/ioonf/ A B C greement with the reserh work previously developed y Sáhez et l. [11] where ws nlyzed the effet of mirooxygention nd wood type on the phenoli omposition nd olor prmeters of red wines. In ddition, Jordão et l. [3] lso deteted new HPLC peks orresponding to new degrdtion produts in solutions ontining mixture of mlvidin-3-gluoside nd ellgi id extrted from ok wood nd lso in solutions ontining mlvidin-3- gluoside nd ok wood extrt. These new ompounds formed inresed slightly during 64 storge dys. Thus, our work points out the importne of wood omponents not only from ok wood speies, ut lso from i nd herry wood speies in the trnsformtion of nthoynins, s well s in retions tht our during the red wine ging in ontt with the different wood speies. It is lso possile tht the new produts formed ould prtiipte in the olor hnges tht usully ourred in red wines ged in wood rrels or in ontt with wood hips. Figure 1. Chnges of the individul nthoynin profile (HPLC) fter mixing model wine solution, ontining nthoynins, with wood hip extrts. (A) model wine solution ontining nthoynin extrt lone; (B) model wine solution ontining nthoynin extrt nd ok wood hip extrt fter 1 dys of storge; (C) model wine solution ontining nthoynin extrt nd ok wood hip extrt fter storge dys; () new pigments formed during storge. y the use of CieLAB oordintes [9]. To distinguish the olor more urtely, the olor differene ws lso lulted using the following formul: ( E = [( L ) 2 + ( ) 2 + ( ) 2 ] 1/2 ). Finlly, the ntioxidnt pity evolution ws investigted y the use of ABTS nd FRAP ssys, pplying the onditions optimized y Rivero et l. []. All nlyses were done in triplite. 3. Results nd disussion 3.1. Individul nthoynins omposition Aording to otined results (Fig. 1), levels of newly formed nthoynins re notle visile fter dys of ontt of model wine solutions with wood extrts. During the storge time onsidered derese of free nthoynins ws deteted in ll model wine solutions (Fig. 1A, 1B nd 1C). In ddition, new pigments re formed in the solutions ontining nthoynin extrt nd wood extrt (Fig. 1C). These new produts formed ourred in ll solutions ontining nthoynin extrt nd different extrts otined from the different wood hip speie used (ok, herry nd i). The numer of new produts formed (inluding the nthoynin pyruvi derivtive produts) nd their onentrtion inrese with the storge time in ll model wine solutions ontining nthoynin extrt nd wood hip extrts. However, the mjority of the diret ondenstion produts formed were deteted in solutions ontining nthoynin extrts nd i nd herry wood hip extrts fter 1 storge dys (dt not show). The results otined in our work re in 3.2. Chromti prmeters Color hnges re one of the gretest modifitions ourring during the wood ging of red wines. Anthoynins re le to rets with ompounds extrted from wood ut lso with other ompounds formed y redox potentil hnges, indued y wood omponents. Under these onditions, nthoynins trnsformtion my led to olor loss or stiliztion, with the orresponding negtive or positive effet on wine qulity. This ft n e vluted through the mesure of olor prmeters s olor intensity, tonlity nd the CieLAB prmeters. The olor intensity evolution quntified in the model wine solutions ontining the different wood hip extrt speies is illustrted in Fig. 2. After dys of storge, generl derese of olor intensity ws oserved in ll the studied mixtures of red wine model solutions nd wood extrts. This result ws lso otined independently of the extrtion time used for otined the different wood extrts (1 nd extrtion dys). However, quntittive differenes were deteted mong smples y ftors, wood extrtion time nd wood type. Higher dereses of olor intensity were lwys oserved in mixtures ontining wood extrts otined fter dys of hips extrtions. So, mixtures with wood extrts otined fter 1 extrtion dys, showed signifint derese of olor intensity only fter dys of storges. The olor redution deteted, my e due to the wood omponents tht were extrted from wood hips tht indue the rte of nthoynin deline nd onsequently indued olor derese (espeilly red olor omponent). Previously Jordão et l. [2] reported mlvidin-3-gluoside delined more rpidly in the presene of ok wood extrt thn lone nd onsequently more evident derese of red olor. In ddition, it hs een reported tht numerous nthoynin dduts re formed during red wine ging in ok wood rrels [12]. These new ompounds presumly hve n influene on the hromti hrteristis of red wines. Another interesting result otined is relted with the impt of the different wood hip extrt speies on olor intensity derese. In ft, the olor derese ws signifintly more pronouned for the red model wine solutions mixed with the herry wood extrts (prtiulrly for the wood extrt otined fter extrtion dys) 2

3 BIO We of Conferenes 9, 013 (17) 40 th World Congress of Vine nd Wine DOI:.1/ioonf/ Color intensity (As. units) 2, 2,1 1,7 1,3 0,9 1 ging dys Wood extrt 1d Wood extrt d L vlues L vlues Extrt 1d+d Extrt d+d 0, Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant. PW+Ant. Model wine solu ons Anthoynins Ch+Ant A+Ant FW+Ant Aw+Ant PW+Ant Color Intensity (As. un s) 2,2 1,9 1,6 1,3 1 0,7 0,4 Wood extrt 1d ging dys Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant. PW+Ant. Model wine solu ons Wood extrt d Figure 2. Color intensity quntified in model wine solutions ontining different wood hip extrts fter 1 nd ging dys. Ch + Ant = Cherry wood hip extrt nd nthoynin extrt; A + Ant = Ai wood hip extrt nd nthoynin extrt; FW + Ant = Frenh wood hip extrt nd nthoynin extrt; AW + Ant = Amerin wood hip extrt nd nthoynin extrt; PW + Ant = Portuguese wood hip extrt nd nthoynin extrt. vlues vlues vlues Extrt 1d+d Extrt d+d Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant PW+Ant vlues Extrt 1d+d Extrt d+d nd espeilly fter storge dys. In wines, severl works [13,14] reported tht the use of herry rrels in wine ging indue fster evolution of wine pigments with quik ugmenttion formtion of derived nd polymeri ompounds. In ddition the use of this type of wood speie demonstrted to provide n environment fvoring oxidtive retions nd, thus inreses the red olor loss, mking it less suitle for longer wine ging periods. Conerning to CieLAB hromti oordintes evlution, Fig. 3 shows the L, nd C vlues otined in model wine solutions fter ging dys. For L vlues (lightness), ll model wine solutions (independently of the extrtion time nd wood speies) showed higher lightness ompred with the initil red model wine. This result is onsistent with the deresed of olor intensity showed in ll red model wine fter mixing with wood extrts. In ft, the derese of olor intensity indues more lightness of the smples. For vlues (redness), lso derese of the red olor omponent vlues ws oserved for ll the mixtures of wood extrts with the red model wine. This result grees the results lredy showed for olor intensity. The derese of red olor omponent ws similr for ll model wine solutions, exept for the model wine solutions ontining herry wood hip nd Frenh ok wood extrt otined fter extrtion dys, where the derese ws more evident. Regrding to the results otined for vlues (hrom), similr tendeny ws lso deteted. Thus, tendeny for hrom vlues derese ws evident for ll red model wine solutions mixed with wood hip extrts, orresponding lso to less olor intensity. Finlly, the vlues otined for olor differene ( E) mong red model wine solution lone nd mixed with the different wood hip extrts (Fig. 4) showed tht Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant PW+Ant Figure 3. CieL hromti oordintes quntified in model wine solutions ontining different wood hip extrts fter ging dys. Ch + Ant = Cherry wood hip extrt nd nthoynin extrt; A + Ant = Ai wood hip extrt nd nthoynin extrt; FW + Ant = Frenh wood hip extrt nd nthoynin extrt; AW + Ant = Amerin wood hip extrt nd nthoynin extrt; PW + Ant = Portuguese wood hip extrt nd nthoynin extrt. ll mixture rised differenes muh higher thn three CieLAB units. Thus, tking into ount tht E vlues of up to three CieLAB units indites olor differenes ppreile to the humn eyes [1], it ould e ffirmed tht the ontt etween nthoynin extrt nd wood hip extrts from different speies led to olor differenes visully pereptile etween in ll model wine solutions. This result onfirms the results lredy show for olor intensity nd the prtil results otined for CieLAB hromti oordintes (Figs. 2 nd 3). In ddition, the high olor differenes results were independently of the wood hip extrts speies. However, the model wine solutions ontining wood extrts otined with longer extrtion time ( dys) showed signifintly higher olor differene vlues. Reently, Cejudo-Bstnte et l. [16], onlude tht the ddition of ok wood hips (during oth fermenttion nd ging) indued lso visully pereptile olor differenes from the erly months of storge of Syrh red wine (vlues mong nd 12) Antioxidnt pity Figure shows the ntioxidnt pity quntified in the different model wine solutions fter ging dys. 3

4 BIO We of Conferenes 9, 013 (17) 40 th World Congress of Vine nd Wine DOI:.1/ioonf/ ΔE vlues ΔE vlues Extrt1d+d Ch+Ant A+Ant FW+Ant AW+Ant PW+Ant Extrt d+d Figure 4. Color differene ( E) quntified in model wine solutions ontining different wood hip extrts fter ging dys. Ch + Ant = Cherry wood hip extrt nd nthoynin extrt; A + Ant = Ai wood hip extrt nd nthoynin extrt; FW + Ant = Frenh wood hip extrt nd nthoynin extrt; AW + Ant = Amerin wood hip extrt nd nthoynin extrt; PW + Ant = Portuguese wood hip extrt nd nthoynin extrt. mm Fe(II) mm Trolox FRAP method Wood extrt1d Wood extrt d Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant. PW+Ant. ABTS method Wood extrt 1d Wood extrt d Anthoynins Ch+Ant A+Ant FW+Ant AW+Ant. PW+Ant. Figure. Antioxidnt pity quntified y two methodologies (FRAP nd ABTS) in model wine solutions fter ging dys. Ch + Ant = Cherry wood hip extrt nd nthoynin extrt; A + Ant = Ai wood hip extrt nd nthoynin extrt; FW + Ant = Frenh wood hip extrt nd nthoynin extrt; AW + Ant = Amerin wood hip extrt nd nthoynin extrt; PW + Ant = Portuguese wood hip extrt nd nthoynin extrt. Aording to the results otined, red model wine lone showed the highest ntioxidnt pity (espeilly onsidering the results otined y the use of FRAP method where the vlues were signifintly higher) in omprison with the results otined for model wine solutions ontining lso the different wood hip extrts. Aording to Rivero et l. [17], gluoside nthoynins re one of the mjor nthoynin group tht determine d d the ntioxidnt pity power of red wines, in prtiulr mlvidin-3-monogluoside. Conerning to the potentil impt of the use of different wood hip extrt speies on ntioxidnt pity, the results otined were not totlly distintive. Thus, slight tendeny for lower ntioxidnt pity vlues were otined for the red model wine solutions mixed with herry wood extrt nd with Amerin ok wood extrt (oth extrted otined fter extrtion dys). Aording to severl uthors [4,18] the use of ok wood indue n inrese of ntioxidnt pity of the red wines during the ging proess s result of polyphenol ompounds extrtion. However, ontrry results were otined y Gortzi et l. [19]. For these uthors, fter onsiderle ging period in ontt with ok wood hips, red wines showed derese of polyphenoli ontent nd onsequently redution of ntioxidnt pity. In ddition, it is importnt to note tht ording to Psrr et l. [] polyphenols extrted from ok wood hips yield lmost 6.4 times higher reduing power omprtive with i hips. Therefore, the ntioxidnt effets exerted y polyphenols do not depend exlusively on their totl mount, ut lso on the different polyphenoli strutures [21]. This ft ould help to explin the similr vlues of ntioxidnt pity found in the mjority of the model wines solutions studied. Proly the use of more extended ging period or higher wood hips onentrtion used to produe the wood hip extrts ould e ftor to onsider in the future to potentite eventul differenes. 4. Conlusions In this work it ws possile to deteted ler influene of the use of different wood hip speies on evolution of the nthoynin omposition nd onsequently on hromti prmeters. This influene ws espeilly detetle y derese of the olor intensity nd espeilly on red olor omponent vlues. In ddition, the ntioxidnt pity showed lso slightly derese of the vlues when nthoynins were put in ontt during dys with wood hip extrts. It ws lso ler tht the time used to otin the wood hip extrts hd prtiulr influene on the results determining n inrese of the vrition of the prmeters nlyzed. This reserh ontriutes to etter knowledge out the olor evolution of red wines when they re ging in ontt with ok wood nd in espeilly when is using new lterntive wood speies, espeilly i nd herry. This spet will e importnt if these wood speies my ome in the future to e uthorized for oenologil purposes. António M. Jordão thnks to FCT (projet UID/Multi/04016/ 16) nd IPV-CI&DETS for their finnil support. Authors lso ppreited the ollortion of the ompnies tht supplied the wood hip smples used in this study (SAI Enology, AEB Bioquími nd J.M. Gonçlves ooperge). Referenes [1] I. Revill, M.L. González-Snjosé, M.C. Gómez- Cordovés, Food Si. Tehnol. Int., (1999) [2] A.M. Jordão, J.M. Rirdo-d-Silv, O. Lureno, Am. J. Enol. Viti. 7, 377 (06) 4

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