R 2009 Institute of Food Technologists doi: 10.1111/j.1750-3841.2009.01063.x Further reproduction without permission is prohibited C A previous study demonstrated that extrusion of sorghum signif- Polymeric procyanidins are poorly absorbed (Donovan and oth- icantly enhanced lower MW (molecularreduced weight) higher procyanidins, MW but procyanidins, includingand others the 2003). polymers Similarly, in (Awika aberry preliminary experiment and with blue- grape pomace,of we monomers and observed dimers compared significantly to higher unextruded controls. levels These fresh berries. While disposaljuice of processing this industry, it waste alsorich is represents source a a of substantial major polyphenolics loss cost withtive of potential to recovery a health the of benefits. procyanidins Effec- other from fruit blueberry by-products) could, pomace therefore, provide (as newhealth-promoting value-added products well and as also serveback as these a valuable model compounds for into the bringing human food chain. ers 2002; Gonthier and othersoligomeric 2003), procyanidins while have monomeric been andand found some others to 2006). be Extrusiontrial absorbed is processes (Shoji one used to ofhance make the the snacks, most overall and commonents. digestibility its indus- It main and simultaneously goal bioavailability performs, iscrushing, of among to pressing, food others, expanding, en- mixing, nutri- drying, cutting, functions and (McDougall sterilizing, and and others soshearing 1996). on, effects In concomitantly particular, at it(Kokini high provides 1993), temperature thereby and modifying pressure acted the upon food by the matrix digestive thattrients. enzymes cannot to Since release be a the majority associatedcluding nu- of blueberries the is in procyanidins a form present notit readily in is available fruits, for imperative absorption, to in- investigate what changes extrusion brings about. RIOR C temperature and 150 rpm screw speed. Extrusion processing ◦ R.L. P AND C) and screw speed (150 and 200 rpm) were tested using mixtures of , ◦ C and 150 rpm screw speed, was 84% higher than the nonextruded con- ◦ ROWNMILLER Vol. 74, Nr. 2, 2009 — ,C.R.B (Prior 2003; Prior and others 2003). Introduction OWARD in vivo ,L.R.H H: Health, Nutrition, and Food HANAL JOURNAL OF FOOD SCIENCE Keywords: anthocyanins, blueberry pomace, catechin, epicatechin, extrusion, LC/MS, procyanidins, tannins rocyanidins, a subclass of flavonoids, consist of monomeric, oligomeric, or polymeric catechins and/or epicatechins. They tents of monomers and dimerstrusion at variables the temperature expense (160 of and large 180 molecular weight procyanidin oligomers and polymers. Ex- ABSTRACT: Blueberryof juice compounds processing shown by-products to aretype possess a II numerous rich diabetes, health and source obesity. benefits,weight of Most compounds including of procyanidins, that protection the which are procyanidins against poorly comprise presentmonomers absorbed coronary in a and and heart blueberry show dimers. group weak disease, pomace, The bioactivity however, objective are compared of large to our molecular the study smaller was molecular to weight identify optimal extrusion variables to enhance the con- blueberry pomace with decorticateddates were white analyzed sorghum for flour procyanidinincreased the at composition monomer, dimer, and a and total trimer ratioest anthocyanin contents of considerably content. monomer at 30:70 Extrusion content, both and temperature of obtained and blueberry 45% at screw pomace speeds. 180 moisture The content. high- Extru- in monomer, dimer, and trimerproximately 40% contents lower apparently for samples were extruded the at result 180 of reduced polymer contents, which was ap- trol. Significantly higher levels of dimer and trimer contents were also obtained under these conditions. Increases reduced total anthocyanin contents bypigments. 33% These to results demonstrate 42% that indicatingdimers extrusion that in processing additional blueberry can pomace. treatments be are used needed to increase to procyanidin retain monomer the and In juice industries, a considerable amount of presscake, or po- 52 and some recent unpublished datapomace from our contains laboratory, 25% blueberry to 50% of the procyanidins present in the fat mobilizing enzymes (Al-Awwadi andsorption others and/or 2005). metabolism Rates of of these ab- procyanidinspact what can is greatly observed im- mace, is left after juiceof extraction the and initial may account fruitcyanidin for weight. contents up of Based to whole on 20% fruits and some juices earlier (Gu and reports others 2003b) on pro- fruits and vegetables, but areand abundantly berries. present Procyanidins in possess cocoa, antioxidant,antibacterial, grape, anti-inflammatory, antiarthritic activities, androle in may the prevention play of heart an disease,cers skin (Joshi important aging, and and others various 2001). can- Previous studiescyanidins also may suggest that improve pro- insulin sensitivity,damage ameliorate associated with free chronic radical age-related disorders, and inhibit are synthesized by all vascular plants and are commonly found in Mention of a trade name, proprietarynot product, or constitute specific a equipment does guaranteeimply by its the approval to U.S. the Dept. exclusion of of other Agriculture products and that may does be not suitable. H MS 20080720 Submitted 9/15/2008,Howard, Accepted 10/31/2008. and Authors Khanal,Arkansas, Brownmiller Fayetteville, AR are 72703,Arkansas with U.S.A. Children’s Nutrition Author Center, Dept. Little Priorinquiries to Rock, is of author AR with Howard (E-mail: 72202, Food USDA-ARS, [email protected]). U.S.A. Direct Science, Univ. of P Composition and Total Anthocyanin Contents of Blueberry Pomace R.C. K JFS Influence of Extrusion Processing on Procyanidin H: Health, Nutrition, & Food ihsrwsed f10ad20rm l ein fteex- the of tempera- regions constant 4 a All at 200 at maintained rpm. extrusion However, were ture. 200 die the and and 150 barrel truder of speeds screw with nlssadteeoe odt r rvddfrte200 the for provided are further data for no extrudates therefore, quality and of analysis amount reasonable not did any It extrudates. produce the of burning caused and frequently extruder //)adajse o10m ihetato ovn.Samples solvent. extraction (70:29.5:0.5, with acid mL acetone:water:acetic 100 to with adjusted times sample and 3 of v/v/v) extracted g were procyanidins 2 short, from In (2006). others and 103 at oven air forced a in h 8 drying by analyzed were of angle an at it to attached die shaped a 90 rod sen- a measuring with had CTW100p extruder Rheomix equipped The sor. and ex- Germany) unit System base PolyLab Karlsruhe, 300p Haake Rheocord Haake, screw twin (Thermo scale truder pilot a using truded a bandadfoe t–20 at mixture frozen pre-extruded and the obtained of was sample it A content experiment. since monomer preliminary highest 45% a in the to the in content to resulted and moisture added extrusion calculated was facilitated Water the content. bring starch to high mixture facilitates its and to procyanidins due of extrusion 2 amounts not of does appreciable total it (a any since basis contain used weight was dry sorghum a white on Decorticated at 30:70 kg/batch). of set ratio U.S.A.) a Mich., at Joseph, speed mixer St. medium kitchen K45SS, a Model Classic in Aid U.S.A.) Tex., (Kitchen Station, College Lab., Univ., Quality A&M Cereal Texas Rooney, L. Dr. of with courtesy Hy- Univ. ATx436xRTx631 mixed A&M brid then (Texas N.Y., sorghum was (Gardiner, white It pomace decorticated grinder. drier milled coffee The hammer freeze a in Genesis U.S.A.). grinding Virtis from before Mass., U.S.A.) a obtained (Milbridge, in was freeze-dried Son seeds was & and skins, Wyman stems, Jasper of consisting mace t1%ad3%mitr otn lge h ahn frequently machine extrudates. the any clogged producing content without moisture 30% and 15% extrusion at that showed pomace pre- blueberry since with used experiment was liminary 45% of content feed-moisture A condition. sion eae opoyndnadatoynncnet r rsne on basis. presented weight are dry contents anthocyanin and procyanidin to related h itr a e aulyadcniuul nsalamounts extrusion. small during in g/feeding) 100 continuously (approximately and respectively. manually mm, fed 20 and was 31.8 mixture of The diameters front and rear with long xrso processing Extrusion preparation Sample pomace. blueberry con- of total moisture and contents feed composition anthocyanin procyanidin 45% on a effects the and at investigate extruder temperature, to screw tent variables, twin a extrusion in the speed, screw studied In we by-products. fruit study, procyanidin-rich this other and ben- blueberry health potential of and efits value nutritional the improve contents, hence procyanidin and en- oligomeric to lower and potential monomeric the the has hance processing extrusion that indicate studies . . . extrusion and procyanidins Blueberry xrcinadaayi fprocyanidins of analysis and Extraction content moisture of Determination rcaiiswr xrce sn oiidmto fKelm of method modified a using extracted were Procyanidins samples extruded and nonextruded all of content moisture The ex- was sorghum white with pomace blueberry of mixture A type, bush (low Blueberry xrso a are u ttmeaue f10 8,200 180, 160, of temperatures at out carried was Extrusion ◦ n esrd3m ndaee.Teti ceswr 4 mm 343 were screws twin The diameter. in mm 3 measured and aeil n Methods and Materials ◦ ◦ tete ce pe lge the clogged speed screw either at C ni ute aoaoyanalyses. laboratory further until C acnu angustifolium Vaccinium ◦ .Aldata All C. ◦ Cextru- )po- ◦ C n 2%frttae,ad8%ad10 o etmr through pentamers for H] 110% – 70% [M and trimer, The 80% decamers. for and 110% tetramer, and for 30% 120% dimer, and for for 90% 25% and and 50% 50% were monomer, Settings respectively. level, trap stability (version ion compound and software as level expressed Control were Esquire They Daltonics). mode the Bruker smart 4.5, using the spectrometer to the according adjusted at of set were was parameters range other scan All The kV. 3.5 was voltage lary eesta agtmse o caes( octamers for masses target as set were 27,addcmr ( decamers and 1297), e stre assfrteinta nterdtcinsegment detection 2H] – their ([M in ions charged trap doubly ion The sensitivity. the their for increase to masses target as set xrse smlirm e iormdyweight. dry kilogram were per Results milligrams 2002). as others expressed and (Gu blueberries previously and described cocoa been have from standards polymer of and characterization oligomer and Fractionation both standard. polymer a as used DP with (contain- procyanidins fraction no ing the procyanidin on polymeric peaks A procyanidin chromatogram. the HPLC of identification others for and used (Gu was cocoa 2003a) from purified decamers through monomers epciey ihadyn a eprtr f350 of temperature L/min, gas 10 drying and psi a nitrogen 50 with were The respectively, nebulizer 2001). the on has others flow-rate which and and pressure stream, (Prior previously effluent described column been the into mmol/L acetate 10 pumping ammonium by accomplished ion- was of procyanidins Enhancement of spectrometer. ization mass apparatus the HPLC into the introduced from was mL/min) HPLC (1 both stream in eluting same B-type. The the or systems. were A- phase mobile were and they conditions whether Elution determine and procyanidins identify to the U.S.A.) mass Mass., trap Billerica, ion Daltonics, Esquire-LC (Bruker Bruker spectrometer a to connected Calif., was autosam- Alto, U.S.A.)—that detector, Palo Technologies, an diode-array (Agilent detector degasser, a fluorescence a solvent compartment, and column a con- thermostat pump, system a quaternary HPLC pler, 1100 a system—Agilent of HPLC sisting another on run Standards pcrmty(HPLC-ESI-MS/MS) spectrometry ionization–mass chromatography–electrospray liquid High-performance ndge fplmrzto eecnutduigaDvlslDiol (250 Develosil a column using conducted were polymerization of degree on were 0.45 Extracts a detector. through fluorescence passed scanning 474 Model Waters and detector a array photodiode 996 Model with Waters equipped a autosampler, U.S.A.) an Mass., Milford, Corp., (Waters system HPLC high-performance to analysis. prior (HPLC) chromatography solution liquid acid acetone:water:acetic of mr eedtce,terrslsaentrpre here. reported not non- are little results their very detected, Since were polymer. amers as presented and were together nonamers grouped than greater nm procyanidins 230 calcu- while individually, were nonamers lated at through Monomers excitation nm. 321 were with at emission peaks and detection Procyanidin fluorescence (2006). others by and monitored Kelm by described as f7%aeoeaddidi peVc(hroaat Holbrook, 25 mL at (ThermoSavant, SpeedVac U.S.A.) 80 N.Y., a in with dried 30% eluted and acetone of then 70% mL were of 40 procyanidins with bound eluted The were methanol. U.S.A.) components Mo., Louis, soluble St. and (Sigma, LH-20 column Sephadex a to on loaded were opst rcaii lgmrsadr containing standard oligomer procyanidin composite A ersnaiesml fteetue leer oaewas pomace blueberry extruded the of sample representative A rcaiiswr nlzduigaWtr lineMdl2690 Model Alliance Waters a using analyzed were Procyanidins o.7,N.2 2009 2, Nr. 74, Vol. × .,5 4.6, ◦ .Tedidrsdewsrcntttdwt mL 2 with reconstituted was residue dried The C. m/z − μ μ itrpirt nlss eaain based Separations analysis. to prior filter M oso ooestruhhpaeswere heptamers through monomers of ions ,Peoee,Trec,Clf,U.S.A.) Calif., Torrence, Phenomenex, m, 41.Teprmtr o eaeswere decamers for parameters The 1441). — < ORA FFO SCIENCE FOOD OF JOURNAL 0 iha vrg Pof DP average an with 10) m/z 13,nnmr ( nonamers 1153), m/z ◦ .Tecapil- The C. 5 o2200. to 150 > 61was 36.1 H m/z 2 53 − )

H: Health, Nutrition, & Food )- + )-epicatechin. Nonetheless, an ob- Figure 1 Representative --- reversed-phase HPLC chromatogram of unextruded (top panel) and extruded (lower panel) blueberry pomace identifying individual peaks of monomer through decamers and polymers, along with A- andcertain B-type oligomeric for procyanidins. Dry matter content of unextruded (55.6%) and extruded (73.5%) pomace need toconsidered be for making direct comparisons in the peak heights of monomer and polymer between theproducts. 2 − min min 70 70 Extruded Unextruded 60 60 The effect of extrusion processing at 2 different tempera- An earlier study reported the presence of both A and B type catechin and which one was ( Effect of extrusion on procyanidin composition cence peak demonstrated the presence2 of monomers 2 co-eluted, monomers. we Since could the not identify which one was ( tures and screw speeds on procyanidin composition of blueberry vious difference in the peaktrimers, size for and monomers (as polymers) wellmaces as between was dimers, apparent in unextruded the chromatogram. andof As oligomers can were extruded detected. be Mass seen, spectral data po- a (Figure series that 2) confirmed some of thesisted oligomers, of at (epi)catechin units least that were the eitherindicating dimers singly or the and doubly linked presence trimers, of con- bothever, A the and A-type B linkages typetamers. were Although procyanidins. no not How- attempt was detected made to inof quantify A- tetramers the and distribution B-type or within dimers pen- and trimers,ual peak components size indicated of that the individ- majority were B-type.or The absence presence of A- or B-typedetermined procyanidins in beyond the hexamers current study. was not dimers and trimers with nopolymers A-type linkages in in lowbush higher blueberries oligomersno or (Gu and concerted others attempt 2002). wasother Although made study to with identify boththe A-type dimers highbush through linkages, octamers and an- consisted lowbush exclusivelyand of blueberries B-type others (Prior found 2001), whichbe is noted that in pomace contrast mayposed to contain to some our whole leaves findings. berries and that Itthe stems procyanidin might as should profile lead op- of to the potentialponent final differences within product each in or procyanidin the oligomer. Moreover, individual differences in maturity com- of the fruit, growing season,tributes genotype, or may other also related at- lead tofinal product. differences in procyanidin profile of the 50 7, 8, 9, and 10 mers 10 7, 8, 9, and – 50 Polymer Polymer 520 A ( 6mer = A 40 40 8mer -test. Significance t 7mer 5mer 6mer 30 30 4B 2A Vol. 74, Nr. 2, 2009 5mer 4B — 2B 3A 2A 4B 4B 3B 1mer 20 20 3A . Cyanidin 3-glucoside (c3g) with a molar 5 . 3B 2A pH4 ) bar to facilitate collision-induced dissociation. 0.05. Results and Discussion 6 700 2B 10 10 − ≤ A – P 2A 10 × 520 1mer A –( JOURNAL OF FOOD SCIENCE FLD1 A, Ex=230, Em=321, TT (RCK5\04190811.D) FLD1 A, Em=321, Ex=230, TT (RCK5\04190825.D) 0 0 pH1 ) 0 50 50 Procyanidin monomers through decamers and polymers were Statistical analysis was carried out in JMP (SAS Inst., Cary, N.C., Total anthocyanins were determined using the pH differential 200 150 100 200 150 100 250 LU LU 54 700 level was set at extinction coefficient of 26900 was used aspressed standard with as results milligrams ex- of c3g equivalents per kilogram dry weight. H Analysis of blueberry pomace procyanidins Statistical analysis Determination of total anthocyanins Blueberry procyanidins and extrusion . . . applied for polymers. Helium was applied asiontrapat1 the collision gas in the identified by comparing the retention timesexternal of standards as peaks well with as their those mass of spectralHPLC-ESI-MS/MS data analyses. Their obtained fluorescence from response curves are shown in Figure 1 and compoundin mass spectra Figure for 2. up Although to tetramers wethrough confirmed decamers retention times with of theirspectral pentamers compound data mass are spectra, providedmade for no to determine mass these the oligomers. mass No unit attempt for was the polymers. The fluores- U.S.A.). Means were separated using Student’s method (Giusti and Wrolstad 2001). In short, 2ples dilutions were prepared; of 1 the with sam- 0.025 M potassiumand chloride buffer the (pH 1) other with sodiumthen acetate equilibrated buffer at (pH 4.5).was room Samples measured temperature were using for aspectrophotometer 15 Hewlett (Hewlett min. Packard Packard, Absorbance 8452A Palo520 photodiode Alto, and array Calif., 700 U.S.A.) at nm in buffers at pH 1 and 4.5, using A collision energy level of 100% was applied. A H: Health, Nutrition, & Food leer rcaiisadetuin... . . extrusion and procyanidins Blueberry iesadtieswr fmxdtp cnitn fbt -adBtps,alttaeswr fB-type. of were tetramers all While B-types), pomace. and blueberry A- in both procyanidins of (consisting oligomeric type certain mixed and of monomeric were of trimers and spectra dimers mass --- Compound 2 Figure Intens. Intens. x10 Intens. Intens. x10 x10 x10 x10 x10 x10 x10 x10 0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 0 1 2 3 4 0 1 2 3 4 0 2 4 6 0 1 2 3 0 2 4 6 6 6 6 6 7 6 7 7 7 400 200 338.8 178.4 190.6 190.4 200 200 392.4 200 283.2 200 400 302.2 Monomer Monomer Monomer Monomer 459.1 200 200 288.8 288.9 367.0 600 300.8 340.5 631.8 400 352.7 430.9 575.0 339.7 400 400 419.9 600 366.8 742.2 510.1 366.9 366.9 250 250 506.6 397.2 800 400 400 407.1 812.7 420.8 722.4 600.7 600 612.7 886.7 600 600 800 477.0 471.8 670.8 492.6 300 962.7 300 713.2 883.0 521.6 1000 546.5 1048.7 954.9 800 Dimer A Dimer B Dimer A Dimer 575.5 575.2 576.5 800 800 Trimer A Trimer B Trimer 1000 1014.5 Tetramer B Tetramer 863.0 865.0 600 600 1152.6 350 350 1200 Tetramer B Tetramer 967.0 1153.6 1000 1000 1000 1298.8 1026.8 1200 1257.8 400 400 1378.3 1105.7 1400 764.9 o.7,N.2 2009 2, Nr. 74, Vol. 780.5 1447.5 800 800 1200 1200 1200 1400 1229.6 1544.8 1446.6 1249.5 450 450 1295.8 1600 1534.1 1658.0 1362.7 1400 1400 1600 — 934.9 1400 1640.7 ORA FFO SCIENCE FOOD OF JOURNAL 500 500 1466.3 1000 1000 1697.0 1804.8 1800 1882.8 1600 1600 1800 -MS, 27.7min (#1015) MS 73 in-M (#1007) S, 27.3m 1600 1845.8 MS,20. n #849) 9 4 8 (# in m .6 0 2 , S -M M,1.min-MS, (#464) 10.4m MS,16. n #682) 2 8 6 (# in m .8 6 1 , S -M -MS, (#267) 5.5min MS,5. n #255) 5 5 2 (# in m .3 5 , S -M -M S, in 18.1m (#722) 550 550 1977.3 -M S, in 8.5m (#402) 2000 1958.2 m/z m/z m/z m/z m/z m/z m/z m/z m/z H 55

H: Health, Nutrition, & Food a c c b c 8 1285 1430 380 1415 335 > ± ± ± ± ± Catboth ◦ DP8 are 26150 16200 23100 16100 15200 > a bc c c b 0.34 0.56 1.8 0.34 0.12 ± ± ± ± ± 6.8 2.3 3.8 0.88 1.61 a c b cd d 0.61 1.4 0.18 1.16 0.94 ± ± ± ± ± composition and content (mg/kg A 6.9 3.7 5.3 13.5 11.4 b a b a b 1.2 3.4 1.6 4.0 0.82 ± ± ± ± ± 25.0 16.9 25.8 12.8 14.3 b bc a bc c 0.05). 1.9 3.8 2.0 9.4 2.0 ≤ ± ± ± ± ± P Changes in content of individual procyanidins are presented in 200-rpm screw speed enhanced DP4 and DP5,ditions other extrusion had con- a negative effect on both. Extrusion at 200 screw speeds clogged and shut down the extruderno frequently, data hence is reported for these treatments. Figure 3. Extrusion enhanced the monomeras 18% contents at from 160/150 as combination little ofas temperature high and screw as speed 80% to atspeed. 180/150 While combination of procyanidins temperature DP280% and and or screw more DP3 under similar were extrusion also conditions, polymer enhanced contents by 41.3 36.0 55.7 34.3 30.8 -test, t C ab ◦ ab b a b 3.3 6.4 6.1 16.7 2.3 ± ± ± ± ± 64.3 52.2 77.4 63.7 58.8 Ctemperature ◦ a abc c bc ab Ctemperatureand ◦ 2.6 7.1 8.9 22.8 27.1 C and the 2nd part represents screw speed in rpm. ◦ ± ± ± ± ± 55.7 68.8 98.7 84.9 Vol. 74, Nr. 2, 2009 106.0 — a c bc a ab 1.1 6.5 8.9 17.0 4.4 ± ± ± ± ± 103 111 156 156 134 a cC c a b 12.4 8.5 7.4 7.8 7.6 ± ± ± ± ± DP1 DP2 DP3 DP4 DP5 DP6 DP7 DP8 DP 0.05), except when extruded at 160 SEM) of blueberry pomace. < ± P B JOURNAL OF FOOD SCIENCE 56 Means within columns with different letters are significantly different (Student’s Procyanidin composition is presented as degree of polymerizationFirst (DP), part in of which the DP1 treatment means represents monomer, temperature DP2 in dimer, and so on. All procyanidins DW, mean H 180/150180/200 276 A 220 B C Table 1 Effect --- of temperature and screw speed duringTreatment extrusion on procyanidin Control160/150160/200 151 171 252 Blueberry procyanidins and extrusion . . . pomace is presented incally Table important 1. monomer as Extrusion well enhanced as dimernificantly the and ( trimer biologi- contents sig- grouped as 1 and described in the text as polymer. and 150 rpm screw speed. The best results were obtained at 180 temperature and 150matogram rpm (Figure 1) of screw the extruded and speed.mace unextruded blueberry A clearly po- demonstrates representative theand chro- substantial some increase oligomers in atlevels monomer the of expense oligomers. of For procyanidins polymersomewhat DP4 and mixed and or some DP5, transition higher the type. While effect 160 was H: Health, Nutrition, & Food rcaiiscudb ovre nomnmr rlwrlvlof level lower or monomers into polymeric converted and be oligomeric could higher procyanidins the of de- much not how could exactly we termine polymers, of purified of level amounts lower sufficient unavail- of the and ability Given extraction. monomer enhanced in of result increase the was the oligomers of part equally is that it 1993), possible (Kokini nutrients associated the release food to the matrix modifying thereby pressure and temperature high at concomi- tantly effects shearing actu- provides extrusion have Since may place. taken compounds of ally the level of lower likely extraction and better is monomer and into it oligomers polymer conditions, of extrusion conversion both different that at reduction contents of polymer degrees varying in the across de- as polymers well the as and of conditions oligomers extrusion light of the In level both. higher of of contents combination creased a of structure third, and and matrix material; the the of dur- disruption effect the shearing causing and pressure, extrusion ing heat, the of effect by combined facilitated the extraction and increased monomer second, into oligomers; oligomers of of level lower level higher or polymer con- First, of product. version extruded the in contents oligomer of level lower chromatogram pomace. the blueberry in extruded procyani- the observed weight of were molecular peaks lower new no to However, converted dins. or may lost which of been most samples, have pomace extruded the of de- most was in neither tected 1), (Figure decamers and nonamers for peaks cence eto h xrso odtosrdcdiscnetsignificantly content its the reduced 160/200 effect, conditions although no ( extrusion DP6, had the speed With of screw 25%. rest and as temperature high per- of few as combination a to as little points as by centage contents ex- their reduced other of oligomers, conditions combination both trusion sense 160/200 enhanced speed the While screw effect. in and mixed temperature oligomers a transition had considered extrusion that be DP4 The could 2004). others DP5 and and Bourvellec Le 2001; polysaccha- others interactions and wall (Renard hydrophobic cell and/or bonding con- to hydrogen polymer irreversibly through rides the bind of may large rest that procyanidins demonstrated the have MW pomace to apple with happened studies what but tents, clear oligomers. of not level lower was or It but monomer 180/200, in or increase 180/150 similar of a that without to similar was speed screw and tempera- of ture combination 160/150 for content Moreover, polymer oligomers. in of reduction level lower and for monomer lower accounted in was increase and the extrusion by monomer during to lost polymer converted all amount been not oligomers, have certain may a polymer While the of extrusion. after considerably decreased . . . extrusion and procyanidins Blueberry P hr r aial osblte o nrae ooe and monomer increased for possibilities 3 basically are There < .5.Wieuetue oaecerysoe h fluores- the showed clearly pomace unextruded While 0.05). a aepeetdetnielse fatoynn.Wiei is it While anthocyanins. of study losses current extensive the prevented in used have (45%) may content 2007). moisture others oth- feed and and higher Camire The 2003; (Camire others extruded and Chaovanalikit and 2002; cereals ers incorpo- breakfast were corn concentrates into blueberry rated when (be- 90%) losses and observed 64% previously extrusion than tween by lower much caused was content 42%) anthocyanin to (33% total in losses The tent. odtos oee,tmeaue ce pe,o hi interac- ( significant their no or had tion speed, screw sig- temperature, However, was conditions. which content, ( anthocyanin higher po- total nificantly Unextruded highest 2008). the others had and mace Brownmiller 2002; Lee others 2000; the others and and into (Skrede expressed operation pressing are the levels following juice appreciable and during steps degraded mashing are juice anthocyanins blueberry for as earlier expected 2003). was reported others This and values Howard 2001; the others dry and than (Prior mg/kg blueberries lower whole 1757 much to is 1023 which from weight, varied pomace blueberry extruded xrso feto oa nhcai content anthocyanin total on effect Extrusion molecu- counterparts. higher weight their lar in decrease weight concomitant molecular a studies lower with procyanidins the these enhances together, extrusion Taken that 2008). demonstrate others and improved was (Gu catechins significantly of bioavailability pigs, weanling to sorghum fed extruded was sorghum When study. current extruded of the level in lower with higher and was study monomer oligomers in recent increment the cur- a 2008), the others to and in (Gu similar extrusion was after study contents magni- polymer rent the in Although reduction 2003). of others tude and (DP oligomers (Awika of contents level polymer higher (DP in contents decrease oligomer concomitant enhanced of a level extrusion lower respectively. sorghum, and 65%, tannin monomer to high the 50% with and study 80% another blue- to In 70% and by seed the contents enhanced monomer grape tested) temperatures extrusion of (lower pomace procyanidins berry on processing extrusion an- be probably would regard. this compounds in bound approach other the of shear release on the conditions and extrusion individual of effect process. the extrusion Determining result the during the conversion was or extraction modulation enhanced such of whether determine not and con- trimer) tents, and dimer possibly (and monomer important bio- logically the enhance to was objective primary our Moreover, oligomers. h oa nhcai otn Fgr )o xrddadun- and extruded of 4) (Figure content anthocyanin total The u rlmnr tde dt o rsne)o h fet of effects the on presented) not (data studies preliminary Our o.7,N.2 2009 2, Nr. 74, Vol. P < (Student’s different significantly different are with letters Bars rpm. in speed ramn ersnstmeauein the ◦ temperature of represents part treatment First speeds. screw and temperature different at extruded contents (mean anthocyanin --- Total 4 Figure n h n atrpeet screw represents part 2nd the and C .5 hntesmlsetue cosall across extruded samples the than 0.05) P > — .5 feto oa nhcai con- anthocyanin total on effect 0.05) ± ORA FFO SCIENCE FOOD OF JOURNAL E nbubrypomace blueberry in SE) t -test, P ≤ 0.05). ≤ ≥ )with 4) )and 5) H 57

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Changes in anthocyanins and polypheno- 80% > Sorghum C and 150 rpm. ◦ Vol. 74, Nr. 2, 2009 — References Conclusions Acknowledgments using animal models. ) and sorghum products alters procyanidin oligomer and polymer distribu- JOURNAL OF FOOD SCIENCE in vivo xtrusion appears tohance be the biologically a important monomers promising and lower level processing of tool to en- Cros G. 2005. Extractscreased cardiac enriched NADPH in oxidase expression differentsulin while polyphenolic resistance, having hypertension, differential families effects and normalize on cardiacJ in- hypertrophy Agric in- Food in Chem high-fructose-fed 53:151–7. rats. bicolor tion and content. J Agric Food Chem 51:5516–21. monomeric anthocyanins, percentprocessed polymeric blueberry color, products. J and Food Sci antioxidant 73:H72–H9. capacity of thocyanins as breakfast cereal colorants. J Food Sci 67:438–41. 58 oligomer contents in fruit by-products. The highest increase ( over control) in monomers was observed at 180 H Al-Awwadi NA, Araiz C, Bornet A, Delbosc C, Cristol JP, Linck N, Ajay J, Teissedre PL, Awika JL, Dykes L, Gu L, Rooney LW, Prior RL. 2003. Processing of sorghum ( Brownmiller C, Howard LR, Prior RL. 2008.Camire ME, Processing Chaovanalikit A, Dougherty and MP, Briggs storage J. 2002. effects Blueberry and on grape an- We thank Dr. L. Rooney of theUniv. Cereal for Quality providing Lab. decorticated at white the sorghum Texas and A&M & Jasper Wyman Son, Milbridge, Mass.,This U.S.A., work for was funded providing by blueberry an Arkansas pomace. Biosciences Inst. grant. E Blueberry procyanidins and extrusion . . . apparent that extrusion has an adversecontent, effect on extrusion total conditions anthocyanin suchstudy may as minimize those the losses used andefits in retain associated many with the anthocyanins. of the present health ben- While dimers and trimerstype were procyanidins, a tetramers, combination and of pentamersthough both were certain A- of extrusion and B-types. conditions Al- B- cananthocyanin significantly contents, reduce the total optimalthat temperature and resulted screw in speed highestlevel of concentrations procyanidin of oligomers resulted monomersthocyanins in than and greater previous retention studies. lower Further of experiments an- to are needed determine what proportiondue of to depolymerization the of increase higherand in molecular how weight monomers much procyanidins was was duethe to matrix the release that of was boundduring disrupted extrusion. compounds Experiments from by are underway the to investigate heat, whether similar results pressure, could and be friction obtainedwhether with such other changes could fruit be by-products translated and toefits perceived health ben- H: Health, Nutrition, & Food