Aromatic and polyphenolic profile of wines from the 

Vranec variet

Ivanova, Violeta

UGD Academic Repository

Aromatic and polyphenolicprofile of wines from the Vranec variety Violeta Ivanova PetropulosFaculty of Agriculture,University “Goce Delčev” – Štip, Republic of N. Macedonia4TH Vranec World Day5th of October, 2022, Skopje, Republic of N. MacedoniaINTRODUCTIONThe grape vine is the source of all wine. Highest level of quality in wine is only possible by starting with the highest quality fruit. Grapes are the largest fruit crop on earth Fairly adaptable plants, growing in a wide variety of soil types, temperatures, climate.  Successfully grown in Europe, the Balkans, Asia, Mediterranean and South Africa, South Australia and New Zealand, most of North America and a good portion of South America.HOW MANY GRAPE VARIETIES ARE GROWN?Several thousand to be precise, but a few hundred are actually used for wine making.The vine plant can produce fruit for up to 100 years.GRAPE VARIETIES IN R. N. MACEDONIARed Grape Varieties: Vranec, Stanušina,Kratošija, Merlot, Pinot Noir, CabernetSauvignon, Cabernet Franc, Karadrka White Grape Varieties:Smederevka, Žilavka, Župjanka,Traminec, Temjanika (Riesling)Chardonnay, Semilion, SauvignonBlanc, Muscat Ottonel, GrenacheBlanc-BelanChardonnayMerlotVranecStanušinaSmederevka ŽilavkaVRANEC variety The most important grape variety used for red wineproduction in R. Macedonia. I represents about 50 % of the total red wine production inthe country. It is grown in all vineyards, mostly in the Tikveš wine region,where more than 80% of the Macedonian vineyards arelocated. The wine produced from this variety has an intense dark redcolour, aroma of plum, sour cherry and wild berries, rich inpolyphenols.Chemical composition of wine A bottle of red wine contains over 1000 chemical compounds Quite amazing when you consider wine is >80% water + alcohol The chemistry of flavour, colour and astringency in wine is enormously complicated.  Many chemical and biochemical pathways are not well understood.Wine is a complex matrix of many components:  Water, Alcohols, Organic acids,Carbohydrates, Aldehydes, Esters  Minerals, Nitrogen compounds  Phenolic compounds  Aromas Vitamins ...............Water ~ 80%Alcohol ~ 12 %Everything else~ 8 %• The volatile composition is a very important factor affecting thewine aromatic attributes and hence its quality.• Some volatile compounds originate from the grapes• Most of them are formed during the fermentation and storageof wines.• Different parameters influence the aroma composition of thegrapes: grape varietal characteristics, light intensity,temperature, soil, climate, degree of maturation, cultivationpractices, etc.AROMA COMPOUNDSAROMA COMPOUNDS Crushing, pressing, fermentation temperature, maceration,yeast strain, SO2, wine dealcoholisation and supercriticalextraction, affect the extraction of grape aroma compoundsin the juice. During wine ageing under different conditions, the volatilecomposition could be changed due to appearance of somevolatiles that could decline the wine aroma quality. Different groups of volatile compounds have been identified in grapes andwines: higher alcohols, esters, aldehydes, lactones, terpenes, C13-norisoprenoids,volatile phenols, fatty acids, carbonyls, sulphur and nitrogen compounds. More than 1000 aroma compounds with different polarities, volatilities andodour impact have been indentified in wines. The main aroma compounds in wine are higher aliphatic alcohols, ethylesters and acetates (mainly formed from the yeast metabolism during thealcoholic fermentation).AROMA COMPOUNDSGAS CHROMATOGRAPHY Gas chromatography/mass spectrometry (GC/MS) is a highlyefficient separation technique for volatiles’ analysis and forcharacterization of the wine bouquet. GC-MS with polar column for separation of components in lowconcentration, as well as, in a complex matrices, as wine is. Extraction methods: solid-phase extraction (SPE), solid-phasemicroextraction (SPME), stir bar sorptive extraction (SBSA), orLiquid-liquid extraction methods using organic solvents(dichloromethane), showing high repeatability and possibility ofcarrying out simultaneous extractions.50 mL wine + 25 mL dichloromethane + 200 μL internal standard of 1-octanol30 min3000 rpm for 15 min at a temperature of 2-4 ºCSeparation of the phasesEvaporation under N2GC-MS analysis (1 μL) Separation - polar capillary column, Carbowax type fromAgilent, (30 m  0.25 mm ID and 0.25 m film thickness)Working parameters:Injector temperature 240 ºC;MS source 230 ºC;MS Quad 150 ºC,Transfer line 280 ºC.40 ºC for 3 min180 ºC at 3 ºC /min.260 ºC with 20 ºC /min260 ºC for 10 minCarrier gas - He with a flow rate of 1.5 mL/min.Splitless mode for injectionMass range of 50–400 m/z, recorded at 1 scan/s.GC-MS analysisAgilent 5975 Mass Spectrometer coupled toan Agilent 6890N Gas ChromatographIvanova et al. Food Analytical Methods, 5, 1427-1434, 2012Ivanova et al. Food and Bioprocess Technology, 6(6) 1609-1617, 2013Analysis of the volatile composition of Vranecwine46 volatile compoundsIn Vranec wine identified and quantifiedIvanova et al. Food and Bioprocess Technology, 6(6) 1609-1617, 2013GC/MS chromatogram of the volatile compounds inVranec wine14 alcohols - secondary products mainly produced duringthe yeast metabolism;19 esters - are formed by esterification of alcohols and acidsfollowed by water molecule elimination;2 fatty acids – products of yeast metabolism, and they couldinhibit the alcoholic fermentation1 furan1 sulphur compound - derived from sulphur-containingamino acids during the microbial transformations, or from theelemental sulphur2 phenols1 lactone3 other compoundsAlcohols(μg/L) Vranec3-Heptanol 72.2Isobutyl alcohol 1001-Pentanol 17363-Methyl-1-pentanol 01-Hexanol 86.1E-3-Hexanol 70.83-Ethoxy-1-propanol 02,3-Butanediol 29.81,3-Butylenglycol 73.93-(Methylthio)-1-propanol 90.4Benzyl alcohol 73.6Phenyl ethyl alcohol 16342,6-Dimethyl-3,7-octadiene-2,6-diol 02,6-Dimethyl-7-octene-2,6-diol 71.82Total alcohols (μg/L) 4040Higher alcohols in Vranec wine0500100015002000Alcohols (μg/L) in Vranec wine 1- pentanol (unpleasant aroma, its esters: pentyl butyrate,smells like apricot, amyl acetate (pentyl acetate), smells likebanana) 2-phenyl ethanol (Saccharomyces cerevisiaemetabolite, pleasant floral odor, rose-like taste) formed by the yeast, from the sugars or from the amino acids.Higher alcohols in Vranec wine0 20 40 60 80 100Isobutyl alcohol1-HexanolBenzyl alcohol3-HeptanolAlcohols (μg/L) in Vranec wine Are major portion of the secondary products of yeast metabolismYeast can produce: isobutanol from valine, isoamyl alcohol from leucine, n-propanol from threonine.3-Heptanol: strong herbaceous odor and apungent, slightly bitter tasteBenzyl alcohol: floral type odor and an fruitytype flavor1-Hexanol: winey fatty fruity wine-like-notes,coconut, berry, fruit-flavorIsobutyl alcohol - sweet whiskey tasteEsters in Vranec wineEsters (μg/L) Vrane wineEthyl propanoate 11.42Ethyliso butyrate 9.85Ethyl butanoate 22.4Isoamyl acetate 30.3Butyl formate 12.5Ethyl caproate 17.3Hexyl acetate 0Ethyl caprilate 19.7Ethyl-3-hydroxybutanoate 17.1Ethyl caprinate 10.4Diethyl succinate 54.2Methyl-4-hydroxybutanoate 0Phenyl ethyl acetate 12.6Diethyl malate 24.4Acetyl glycineethyl ester 12.5Ethyl palmitate n.d.E-11-Hexadecanoic acid ethylester n.d.Succinic acid, 2-hydroxy-3-methyl-diethylester 23.3Total esters (μg/L) 328Esters in Vranec wine0 10 20 30 40 50 60Diethyl succinateIsoamyl acetateDiethyl malateEthyl butanoateEthyl caprilateEthyl caproateEsters (μg/L) in Vranec wine  Ethyl caproate (ethyl hexanoate) - green apple aroma Ethyl caprilate (ethyl octanoate) - strong caramel and fruity odor (apricot) Diethyl malate - floral and fruity aroma, over-ripe, peach and prune Isoamyl acetate - pleasant fruity notes (banana and strawberry aroma) Diethyl succinate - characteristic volatile compounds of the malolactic fermentation in young wines,its concentration increases during wine storage and aging, floral and fruity aroma.0.010.020.030.040.050.060.070.080.0TotalalcoholsTotalestersTotalterpenesTotalacidsTotalfuransTotalsulphuriccomTotalphenolsTotallactonesAromatic profile of VranecIn general: complex aroma profile of Vranec winesComparison of aromatic profile of Vranec, Merlot and Cabernet Sauvignon 0100020003000400050006000VRANEC MERLOT CABERNET SAUVIGNONTotal alcohols (μg/L) 05001000150020002500Vranec Merlo CabernetSauvignonPhenyl ethyl alcohol (μg/L)95100105110115Vranec Merlo CabernetSauvignonIsobutyl alcohol (μg/L)MerlotMerlotComparison of individual aromatic compounds in Vranec, Merlot and Cabernet Sauvignon 0 10 20 30VranecMerloCabernet SauvignonIsoamyl acetate (μg/L) (banana)0 5 10VranecMerloCabernet SauvignonPhenyl ethyl acetate (rose)0 10 20VranecMerloCabernet SauvignonDiethyl malate (μg/L)(over-ripe, peach and prune)262264266268270272274276278280VRANEC MERLO CABERNET SAUVIGNON Total esters (μg/L)abernet auvignonMerlotVranecCabernet SauvignonMerlotVranecCabernet SauvignonMerlotVranecMERLOT             Phenolic composition of wineVery important components in wine and grapes responsible for the quality of wine, Beneficial effects on health: antioxidant, antimicrobial, anticancer ... Determine the color, taste, astringency and bitterness of the wine. They are responsible for the differences between red and white wines, especially thecolor and taste of reds. These substances are present in different parts of the grapes and are extracted duringvinification.Structure of phenolPHENOLIC COMPONENTSFLAVONOIDSAnthocyaninsFlavan-3-olsFlavonolsFlavons. Flavanons....NON-FLAVONOIDSPhenolic acidsStilbensSkin: anthocyanins. Tanins, flavonolsPulpSeeds: flavan-3-olsMONOMERSAnalytical technologies for analysis of polyphenolsHPLC-DADHPLC-DAD-MS (high-performance liquid chromatography coupled with diode-array detector, mass detector)HPLC-DAD analysis of Vranec wineanthocyaninsflavan-3-ols/hydroxybenozic acids hydroxycinnamic acids derivativesQuantification of anthocyanins in Vranec wines during maturationAnthocyanins (mg/L) Vranec wineTime of maceration 3 days 6 days 9 daysDp-Glc 5.88 12.2 10.3Pt-Glc 30.4 48.6 43.2Pn-Glc 9.13 21.1 17.8Mv-Glc 485 649 595Total Glc 531 732 667Pt-AcGlc 3.65 5.89 5.63Pn-AcGlc 6.30 8.53 8.48Mv-AcGlc 73.3 102 94.8Total AcGlc 83.3 116 109Pn-coumGlc 3.56 6.92 5.31Mv-coumGlc 53.5 74.1 59.2Total coumGlc 57.1 81.1 64.5Total Anthocyanins 671 929 84001002003004005006007008003 days 6 days 9 daysTotal Glc Total AcGlc Total coumGlc020040060080010003 days 6 days 9 daysTotal Glc Total AnthocyaninsQuantification of phenolic acids in Vranec wines during macurationPhenolic acids Vranec winesTime of maceration 3 days 6 dys 9 daysProtocatecuic acid 47.6 n.d. 26.7Gallic acid 59.9 187 170Syringic acid 32.5 24.4 37.1Total HBA 140 211 234p-Coumaric acid 14.1 12.8 8.40Caftaric acid 195 166 148Coutaric acid 23.3 29.4 25.5Caffeic acid 10.9 10.9 16.2Fertaric acid 18.2 22.7 19.5Total HCA 262 242 218Total Phenolic acids 402 453 451(+)-Catechin 20.5 220 2510501001502002503 days 6 dys 9 daysGallic acid Total HBA01002003004005003 days 6 dys 9 daysCaftaric acid Total HCA Total Phenolic acidsComparison of Vranec with Stanušinaand Cabernet SauvignonAnthocyanins Hydorxycinnamic acids02004006008001000Stanušina CabernetSauvignonVranecTotal Glc Total anthocyanins0100200300400500600700Stanušina CabernetSauvignonVranecCaftaric acid Total HCA Total phenolic acidsVranec winesTime of maceration 3 days 6 days 9 daysTP (mg/L, GAE) 913 1045 1084CI 5.81 4.24 5.51H 0.44 0.53 0.51AA (mg/L, TE) 107 109 109Correlation between total phenolsand antioxidant activity of Vranecwines020406080100120140Stanušina Vranec CabernetSauvignonAA (mg/L, TE) Comparison of antioxidant activity of Vranecwines with Stanušina and Cabernet Sauvignon Complex aroma profile of Vranec wines determined by GC-MS Complex polyphenols profile of Vranecwines determined by HPLC High antioxidant potential Further and continuous research on aromatic and polyphenolic profile of Vranec wine.Organizers of the 4th Vranec world dayWines of MacedoniaThank you for your attention!We have a brandMacedonia has a brandVRANEC is our brand and pride

Aromatic and polyphenolic profile of wines from the Vranec variety

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Aromatic and polyphenolic profile of wines from the Vranec variety

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