Interntionl Journl of Food Science Volume 2013, Article ID 968020, 6 pges http://dx.doi.org/10.1155/2013/968020 Reserch Article Chemometrics of Whet Composites with Hemp, Teff, nd Chi Flour: Comprison of Rheologicl Fetures Mrie Hrušková, Ivn Švec, nd Ivn Jurinová Deprtment of Crohydrtes nd Cerels, Institute of Chemicl Technology in Prgue, Technická 5, 166 28 Prgue 6, Czech Repulic Correspondence should e ddressed to Ivn Švec; ivn.svec@vscht.cz Received 21 Decemer 2012; Revised 7 Ferury 2013; Accepted 18 Ferury 2013 Acdemic Editor: Zoulikh Mche-Rezzoug Copyright 2013 Mrie Hrušková et l. This is n open ccess rticle distriuted under the Cretive Commons Attriution License, which permits unrestricted use, distriution, nd reproduction in ny medium, provided the originl work is properly cited. The mixol, rheologicl device developed recently, comines pproved frinogrph nd mylogrph test procedures. Anlysing whet flour composites with hemp, teff, or chi in terms of ll three mentioned rheologicl methods, correspondence of frinogrph, nd mylogrph versus mixol fetures ws exmined y principl component nlysis. The first two principl components, PC1 nd PC2, explined 75% of dt sctter nd llowed stisfying confirmtion of presumed reltionships etween frinogrph or mylogrph nd mixol prmeters. Dough development time nd stility were ssocited with gluten strength (C1 torque point) nd lso dough softening (mixing tolernce index) hd link to protein wekening (C1-C2 difference). In the second mentioned cse, mylogrph viscosity mximum nd mylse ctivity (C3-C4) closeness ws verified. Strch nd strch gel properties during mixing (C3, C3-C2, nd C4) ffect dough viscosity (C1) nd rheologicl ehviour (dough development time nd stility). Another importnt finding is unequivocl distinguishing of the composite susets (of hemp, teff, nd chi ones) y the used rheologicl methods nd sttisticl tretment of multivrile dt. 1. Introduction Addition of nontrditionl components offers new possiility of whet flour properties nd could e performed y milling product from hemp, teff, nd chi seeds. By the wy, mentioned components lso improve nutritionl vlue of products owing to protein content nd further positive ingredients for helth. Hemp (Cnnis stiv) is plnted s two suspecies, nmely, ssp. cult nd ssp. indic. The ltter is clled hsh hemp nd elongs to foridden rw mteril with respect to intoxicting sustnces production. Hemp flour composition depends on vriety nd plnting loclity nd differs ccording to preprtion nd deftting. Protein, ft, nd strch rtes re known to e 30 33%, 7 13%, nd pproximtely 40%, respectively. It contins significnt level of et-crotene nd vitmins B 1 nd E. Considering minerl component spect, enefit could e found in higher portion of iron nd zinc [1]. Approximtely two-thirds of hemp proteins is composed y edestin, elonging to low moleculr weight gloulins. Teff (Ergrostis tef ) is clssified into cerel group of the Pocee (Grminee) fmily. As reported y Gomez nd Gust [2], min producer is Ethiopi with nnul production of 1 million tons (20% of locl cerels yield). Flt red injer (inger) domintes mong other culinry tretments, nd it is mnufctured from thin fermented dough with portion ofwhetflour.becuseofitstinyseeds,wholemelflour is chrcterised y high rte of coting lyers nd sprout, resulting into higher content of insolule polyscchrides. Proteins hve nongluten nture nd owing to previling portion of prolmins elong to esily digestile ones. From nutritionl enefit viewpoint, high minerls content is cited (minly iron, clcium, phosphorus, nd copper) nd B 1 vitmin. Chi (Slvi hispnic L.) is n nnul her of the Lite fmily, producing seeds which were one of the sic foods from the Aztec civiliztion. Now, the min producers elong to Argentine, Columi, nd Peru. The composition includes minerls, out 20% protein, 30 32% ft, 30 40% polyscchrides (insolule fire s the importnt portion), nd 2-3% fructooligoscchrides [3]. The ftty cid of the oil
2 Interntionl Journl of Food Science Tle 1: Frinogrph nd mylogrph test results of whet flour composites. Smple Frinogrph Amylogrph DDE (min) DST (min) MTI (FU) AMY (AU) (A) Effect of 5 nd 20% of hemp K1-05 6.00 8.50 30 490 K1-20 5.50 11.50 40 365 K2-05 3.00 10.00 30 500 K2-20 8.00 11.00 45 380 K3-05 3.50 8.00 40 565 K3-20 6.00 7.00 50 680 (B) Effect of 10 nd 30% of teff R1-10 9.50 11.00 60 400 R1-30 5.00 6.50 120 620 R2-10 7.50 9.25 140 350 R2-30 1.75 3.00 140 510 (C) Effect of 2.5 nd 5.0% of chi Ch1-2.5 7.50 19.00 20 260 Ch1-5.0 9.00 19.00 20 260 Ch2-2.5 8.0 20.00 40 310 Ch2-5.0 11.0 20.00 40 330 DDE dough development, DST dough stility, MTI mixing tolernce index; FU frinogrph unit. AMY mylogrph viscosity mximum; AU mylogrph unit. -: column mens relted to lterntive crop signed y sme letter re not significntly different (P > 0.05). ws found to consist mostly of C16:0, C18:0, C18:2, nd C18:3. Both forms (lck nd white) exhiit high ntioxidnt ctivity due to the presence of phenolic compounds nd tocopherols. Chi seeds hve een pproved y the EFSA nd my e used s novel food ingredients in kery products in the EU t mximum 5% [4]. A gol of the presented work ws n investigtion of frinogrph nd mylogrph versus mixol fetures comprility, performed y correltion nd hierrchicl cluster nlyses. Torque points C1 nd C2, descriing mixing prt of the Mixol test, could hve reltionships to for exmple, frinogrph dough development time or mixing tolernce index, while difference C3-C4 should e correlted with mylogrph viscosity mximum. Secondly, three tested whet flour composite susets (whet flour with hemp, teff, or chi ones) should e distinguished y sttisticl mens ccording theinfluencesoflterntiveflouronrheologiclehviour. For this purpose, principl component nlysis ws used, studying influences of lterntive flour nd ddition level fctors. 2. Mterils nd Methods 2.1. Mterils. Whetflourusedscompositessews of commercil origin, otined from industril mill Delt Prgue in 2010, nd is chrcterised y low sh (0.59%) nd quite high protein contents 12.97%. Hemp flour smples K1, K2, nd K3 were produced lso in the yer 2010. The former two hemp flour smples were gined s conventionl plnting regime commodity (E. Citterrtová s compny, Czech Repulic).Onthecontrry,thesmpleK3wsprepredfrom hemp grin red under ioregime conditions (Hnf & Ntur, Germny). Whetflourreplcementwsselectedonlevelsof5%, 10%, 15%, nd 20% identiclly for ll three hemp mterils. Teff flour R1 nd R2 smples were produced y Toi Teff UK Ltd., nd they could e identified ccording their white nd rown otnicl type. Whet flour replcement rtios were 10, 20, nd 30% for oth teff types. Chi flour Ch1 nd Ch2 smples were prepred from conventionlly nd orgniclly produced white nd drk chi seeds, ought from Aid Orgnic nd Country Life CZ compnies, respectively. Chi seed smples originted in Mexico. With respect to EU legisltion, sustitution levels were chosen s 2.5% nd 5.0% of whet flour. Mixed composites were signed y comintion of lterntive flour type nd its ddition level, for exmple, K2-15 mens rtio of 85%/15% (w/w) of whet nd K2 hemp flour, respectively. 2.2. Methods. Using fctor 5.7, protein content (PRO) ws determined ccording to the Kjeldhl s method (ČSN ISO 1871). The frinogrph nd the mylogrph test ws performed following ČSN ISO 5530-1 nd ICC 126/1, respectively. Oserved fetures were dough development time nd dough stility in min (DDE nd DST, resp.) together with mixing tolernce index (MTI, frinogrph unit); DDE nd DST express protein strength t dough mixing nd protein resistnce ginst dough overmixing. From mylogrph curve record, the mylogrph viscosity mximum (AMY, mylogrph unit) ws considered; it hs reltion to strch physicl-chemicl stge nd it corresponds to mylses
Interntionl Journl of Food Science 3 Tle 2: Mixol test results of whet flour composites. Smple Mixol C1 (N m) C2 (N m) C3 (N m) C4 (N m) C5 (N m) (A) Effect of 5 nd 20% of hemp K1-05 0.98 0.50 2.01 1.59 2.42 K1-20 0.95 0.49 1.91 1.25 1.86 K2-05 1.02 0.51 2.03 1.56 2.17 K2-20 0.94 0.46 1.90 1.32 1.84 K3-05 1.06 0.48 1.99 1.60 2.34 K3-20 0.94 0.41 1.80 1.41 2.08 (B) Effect of 10 nd 30% of teff R1-10 1.02 0.37 1.79 1.26 1.71 R1-30 0.99 0.26 1.79 1.32 1.88 R2-10 0.93 0.20 1.58 0.94 1.44 R2-30 1.04 0.21 1.57 1.12 1.47 (C) Effect of 2.5 nd 5.0% of chi Ch1-2.5 1.21 0.58 2.05 1.75 2.55 Ch1-5.0 1.19 0.53 2.00 1.69 2.57 c c Ch2-2.5 1.16 0.54 2.01 1.72 2.53 c Ch2-5.0 1.22 0.56 2.03 1.68 2.52 C1 C5: Mixol torque dt. c: column mens relted to lterntive crop signed y sme letter re not significntly different (P > 0.05). Tle 3: Correltion nlysis etween mixol, frinogrph nd mylogrph test prmeters. Prmeter C1 C2 C3 C4 C5 C12 C32 C34 C54 DDE ns ns ns ns ns ns ns ns ns DST 0,73 0,68 0,63 0,63 0,67 ns ns ns 0,65 MTI ns 0,96 0,93 0,76 0,79 0,77 0,57 ns 0,76 AMY 0,46 ns ns ns ns ns ns ns ns C1 C5, nd their pir differences C1-C2 (C12), C3-C2 (C32), C3-C4 (C34), C5-C4 (C54) mixol torque dt. DDE dough development, DST dough stility, MTI mixing tolrnce index. AMY mylogrph viscosity mximum.,, reltionships significnt t P = 95%,99% nd 99.9%, respectively; ns non-significnt. ctivity. On the mixol, predefined protocol Chopin+ ws used, with the test settings corresponding to user s mnul nd pulished erlier [5]. The test settings comine kneding speed 80 min 1, kneder temperture 30 C, heting rte 2 C/min, nd totl nlysis time 45 min. Course of whet dough ehviour s well s the composite dough ones ws descried y five sic torque points (C1 C5, N m) nd four pir differences (C1-C2, C3-C2, C3-C4, nd C5-C4, revited s, e.g., C12). For sttisticl tretment of mesured dt, the softwre Sttistic 7.0 (Sttsoft, USA) ws used. Within the pirs hempteff, teff-chi, nd hemp-chi composites, differences etween recorded rheologicl feture mens s well s their sctters similrity were tested y pir Student s t-test on P=95%. By liner correltion nlysis, correspondence etween mixol versus frinogrph nd mylogrph dt ws explored (P = 95%, 99%, nd 99.9%). For vriles closeness exmintion, oth principl component nlysis (PCA) nd hierrchicl clustering were employed. Histogrm, the second method output,wsuiltineuclidenspceccordingtothefrthest neighourhood clustering lgorithm. 3. Results nd Discussion 3.1. Properties of Tested Flour Composites 3.1.1. Protein Content. Composite K1 nd K2 susets re chrcterised y PRO slightly higher thn common level of the Czech whet, tht is, from 13.11 to 14.82% for smples with 5% nd 20% of hemp flour. Blends contining hemp K3 type were somewht richer in the component; determined limits were 13.46% nd 15.94% for dequte lends. Pure teff flours R1 nd R2 hd the lowest PRO etween tested nontrditionl mterils; with respect to this, their ddition did not ment nutritionl enefit in the former cse, PRO oscillted round 12.57% nd round 13.06% in the ltter. According to smllest mount dded (2.5% nd 5.0%), whet flour enhnced y chi ones demonstrted very slight increse of PRO from 10.97% to 11.21%, respectively, independently to Ch1 or Ch2 type. 3.1.2. Rheologicl Chrcteristics. Frinogrph dt in Tle 1 show diverse influence of tested lterntive flour types
4 Interntionl Journl of Food Science 1 3 PC2 (19%) 0 MTI C34 AMY C12 DDE C32 C1 DST C3 C2 C54 C5 C4 1 1 0 1 PC1 (56%) PC2 (19%) 0 R2-30 R2-10 R1-30 R1-20 R1-10 K1-15 K1-10 K2-05 K1-20 K1-05 K2-15 K2-10 K3-2 0 K3-05 K2-20 K3-10 K3-15 Ch1-2.5 Ch1-2.5 R2-20 Ch1-5 Ch1-5 3 6 0 6 PC1 (56%) () () Figure 1: Comprison of rheologicl ehviour of whet-hemp (K1, K2, K3), whet-teff (R1, R2), nd whet-chi (Ch1, Ch2) composite flour y PCA. () vriles loding plot frinogrph dt: DDT: dough development time, DST: dough stility, MTI: mixing tolernce index; mylogrph dt: AMY: viscosity mximum; Mixol torque dt: C1 C5, nd their pir differences C12, C32, C34, nd C54. () Smples score plot. Dissimilrity (%) 0 20 40 60 80 100 C1 DST DDE C2 C3 C4 C5 C54 C32 C12 MTI AMY C34 0 2 4 6 8 10 Eucliden distnce Figure 2: Cluster nlysis etween frinogrph, mylogrph, nd mixol prmeters. Frinogrph dt: DDT: dough development time, DST: dough stility, MTI: mixing tolernce index; mylogrph dt: AMY: viscosity mximum; Mixol torque dt: C1 C5, nd their pir differences C12, C32, C34, nd C54.
Interntionl Journl of Food Science 5 Tle 4: Proportion (%) of explined vrition y first three principl components (PC s). Prmeter PC1 PC2 PC3 C1 36 53 3 C2 87 6 3 C3 88 9 0 C4 88 0 11 C5 92 0 6 C12 21 65 10 C32 45 11 6 C34 25 26 43 C54 83 0 1 DDE 12 27 29 DST 62 19 15 MTI 76 14 2 AMY 14 19 53 Totl 56 19 14 C1 C5, nd their pir differences mixol torque dt. DDE dough development, DST dough stility, MTI mixing tolernce index, AMY mylogrph viscosity mximum., singnificnt pir correltionship etween qulity prmeter nd proper principl component. on whet composite king qulity. Shorter the DDE nd the DST times were oserved only in cses of K1 nd teff supplements, independently to their white/rown type. Such king qulity chnge ment lso n increse in the MTI vlues, which were verifily the highest just for R1 nd R2 smples. Furthermore, chi mixtures could e clerly distinguished from the hemp ones in the DST (pproximtely twofoldwithinthechisusets). During the mylogrph test, viscosity of flour suspensions contining oth tested chi types ws recorded on pproximtely hlf level thn other composites. Compring hemp nd teff susets, suspensions viscosity mximum incresed in the former nd reversely diminished in the ltter cse s ddition level of lterntive flour incresed (Tle 1). 3.1.3. Mixol Profile. Interprettion of Mixol curves determined in Chopin+ mesurement mode ws pulished previously [5 7]. The first two mixol curve prmeters, C1 nd C2, re relted to protein king strength. According to C1 nd C2 torque points, nlysed composite susets could e prtilly nd completely distinguished (vriility - nd - c in Tles 1 nd 2, resp.). During chi-dough mixing, the highest resistnce nd the lowest dmge of protein structures ws provly reveled correspondingly to their DST vlues. On the other hnd, gluten-like proteins in oth teff flour smples were the wekest (Tle 2). Indirect exmintion of nylses ctivity is represented y further three torque prmeters, C3 s well s C4 during heting nd C5 during cooling phse of the mixol test. ANOVA results in Tle 2 summrise roder extent of lterntive flours influence the strongest impct ws significntly determined for oth chi Ch1 nd Ch2 smples. 3.2. Sttisticl Anlysis 3.2.1. Correltion Anlysis. Withrespecttothepperim, Person correltion mtrix (s n explortion method) ws clculted firstly. Considering three proility levels (of 95, 99, nd 99.9%), the frinogrph test is stisfyingly represented ythedstndthemtifetures(tle3). No significnt reltionships etween the DDE nd the Mixol fetures could e explined y reversl hemp nd teff versus chi effect on this dough property. The sme reson (due to inconsistency within, e.g., hemp suset) leds to only one significnt reltionship of the AMY nd the C1 (r = 0.46, P = 95%). According to interntionl stndrds, mylses ctivity could e descried y the reference mylogrph test, so y the screening method Flling Numer. Codină etl. [7] mentioned tight ssocition of the Flling Numer with strch geltiniztion C3, mylolytic ctivity C4, nd strch retrogrdtion C5 (r = 0.877, 0.794 nd 0.907) nd their differences (C32 nd C54, r = 0.878 nd 0.953, resp.) within thesetof60romninredfloursmples. 3.2.2. Principl Component Anlysis (PCA). As known, dt for the PCA must e intercorrelted nd oserved susets should e chrcterised y similr dt vrince. Links mong ll 13 determined vriles were presented ove, nd suset sctter comprility ws tested y the pir Student s t-test. Mesured feture verges of hemp-teff, hemp-chi, nd teff-chi were not different in 9 cses, nd dissimilr suset sctters were found in 11 cses of 39 in totl (dt not shown). Summrised, the PCA method could explin vriility within the set correctly. Dt vrince ws explined from 89% y the first three principl components (PCs), from 56%, 19%, nd 14% y PC1, PC2, nd PC3, respectively (Tle 4). The mixol nd frinogrph mixing prmeters were ssocited together long the PC1 xis, groups of DDE-DST-C1 s well s MTI- C12 represent the initil kneding phses of nd dough consistence diminishing during the tests (Figure 1()). Connected lso to the PC1, grouping of AMY-C34 nd their link to torque points C4-C5-C54 reflects mylses ctivity nd consequences of their ction ltogether. The third fetures comintion is remrkle for DDE-DST nd lso five Cs s well s C32 nd C54 enzymtic strch degrdtion results into dough resistnce wekening. The findings correspond to conclusions mentioned in [7] C1 hd link to dough stility during mixol test in Simultor regime. Authors furthermore documented on the PC1 PC2 plot, nd C3, C4, C5 together with C32 nd C54 were ssocited with the Flling Numer testing. Studying effect of composites chemicl constitution, lso ll three tested susets were successfully distinguished y comintion of three employed rheologicl tests nd the multivrile explortive sttistics. A dominnt influence of tested lterntive crop is unequivocl in the PC1 PC2 plot, over the crops conventionl/orgnic origin, white/rown type or dded mount fctors (Figure 1()). As discussed previously, for exmple, hemp nd chi composites differed in PRO nd DST or estimted mylolytic ctivity (AMY).
6 Interntionl Journl of Food Science 3.2.3. Hierrchicl Clustering. Possile sustitutions within the rheologicl feture groups were further tested y cluster nlysis. Bsed on dt pretreted y stndrdistion (due to diversescles),histogrmwsuiltintheeuclidenspce using the frthest neighourhood lgorithm. Within Figure 2, three suunits could e identified in ccordnce with the PCA method results (e.g., DDE-DST-C1 in lue). For primry pir clusters (C1-DST, C12-MTI, C2-C3, nd C4-C5), the fetures sttisticl similrity ws determined t lest 60%. To summrise, distnce of 9.07 units (100% dissimilrity) ws evlutedetweenthemtindthec2rheologiclfetures. 4. Conclusions [4] E. Iglesis-Puig nd M. Hros, Chi in Europe: new ingredient for kery products, Act Alimentri,vol.420,pp.74 77, 2011. [5] M. Hrušková, I. Švec, nd I. Jurinová, Chnges in king qulity of composite whet/hemp flour detected y mens of Mixol, Cerel Reserch Communictions, vol. 41, no. 1, pp. 150 159, 2013. [6] A. Dut, A new AACC interntionl pproved method to mesure rheologicl properties of dough smple, Cerel Foods World,vol.55,no.3,pp.150 153,2010. [7] G. G. Codină, S. Mirones, D. Bordei, nd A. Lehu, Mixol versus lveogrph nd flling numer, Czech Journl of Food Sciences,vol.28,no.3,pp.185 191,2010. Presented study experimentl design included comprison of three rheologicl methods result, ssessed for whet flour lends with hemp, teff, nd chi, nd the PCA method used for fetures closeness determintion s well s discrimintion of the three tested composite susets. Frinogrph, mylogrph, nd mixol dt hve shown sic differences in composite dough rheologicl ehviour, tht is, in kery potentil of these mixtures. Correltion nlysis prtilly signified some links etween prmeters of these three tests, nd principl component nlysis confirmed presumed reltionships in greement with conclusion pulished y other uthors. Within 75% of explined vriility (PC1 PC2 plne) nd considered frinogrph chrcteristics, tight ssocitions were reveled out etween dough development time or stility nd C1, nd etween mixing tolernce index nd the difference C1-C2. Amylogrph viscosity mximum ws connected with C3, C4 nd C5 torque points (nd lso with C3-C2, C3-C4, nd C5-C4 differences), which correspond to mylses ctivity nd strch gel properties during heting nd cooling phse of the mixol test. Levels of those torque points (C3, C4, nd C5) corresponded to dough consistency chnges (i.e., resistnce ginst mixing), so reltionships to frinogrph dough development time nd stility. Allthesefindingswereconfirmedyhierrchiclclustering in Eucliden spce, ecuse mentioned fetures groups were found in uilt histogrm. Conflict of Interests Authors herey declre tht they do not hve direct finncil reltion with the commercil identities mentioned in the pper, so there is not ny conflict of interests. References [1] C. Perlín, Hemp s food, Výživ Potrviny, vol. 57, no. 4, pp. 121 122, 2002 (Czech). [2] M.I.GomezndS.C.Gust, Millets, inencyclopedi of Food Sciences nd Nutrition, L.TrugondP.M.Fingls,Eds.,pp. 3974 3979, Elsevier, New York, NY, USA, 2nd edition, 2003. [3] D. E. Pszczol, Seeds of success, Food Technology,vol.66,no. 11, pp. 45 55, 2012.
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