Phenolic profile of Macedonian red wines

Wine possess a variety of recognized beneficial effects on human health, such as anti-inflammatory, antimicrobial and anti-aging effects, as well as prevention of cardiovascular diseases. All these effects are due to the high content of phenolic compounds, such as stilbenes, anthocyanins, flavonols, flavan-3-ols and phenolic acids. In this study, red wines from Vranec, Cabernet Sauvignon and Merlot varieties (V. Vinifera L.) have been analysed using high-performance liquid chromatography coupled with diode array detector and on line mass spectrometry (HPLC-DAD–ESI-MS and MS/MS) in order to determine their phenolic profile. All wines presented a complex phenolic profile represented by anthocyanins, pyranoanthocyanins, flavonols, hydroxycinnamic acids and their derivatives, stilbenes, gallic acid and flavan-3-ols. Vranec wine, which is characterized with deep red colour, showed highest concentration of all phenolic families compared to Cabernet Sauvignon and Merlot wines, indicating the important role of variety in differentiation of phenolic composition

Efecto de la microoxigenación después de la fermentación maloláctica en el aroma y composición fenólica de un vino cencibel

Se microoxigenó un vino Cencibel, variedad autóctona en la región de Castilla-La Mancha, de contenido polifenólico medio (IPTde50), durante dos meses después de la fermentación maloláctica, con una dosis de oxígeno total de 7mL/L, y se comparó con un vino control de elaboración tradicional. Se evaluaron los parámetros de compuestos volátiles (GC/MS) y compuestos responsables del color de los vinos (HPLC/MS y espectrofotometría), así como la evaluación sensorial realizada por catadores expertos. Se apreciaron diferencias organolépticas entre los vinos control y microoxigenados, no encontrándose apenas variaciones en los compuestos responsables del aroma y del color.Ministerio de Educación y Ciencia (España): proyecto AGL 2004-0720

Copigmentación y piranoantocianos. El papel de los flavonoles y los ácidos hidroxicinámicos en el color del vino tinto

Los antocianos monómeros y otros compuestos de naturaleza fenólica juegan un papel determinante en la definición del color del vino tinto y de su evolución durante el envejecimiento, en función de múltiples fenómenos de copigmentación

Estudio sobre las reacciones de malondialdehido con amino azucares y sus posibles implicaciones en la reaccion de oscurecimiento no enzimatico (reaccion de maillard)

El malondialdehido es una sustancia natural que se produce en la peroxidacion lipidica y que se encuentra ampliamente distribuido en los tejidos de mamiferos y en los alimentos ricos en lipidos parcialmente oxidados. Debido a su naturaleza quimica muestra una gran reactividad hacia los compuestos aminicos. En medios fisiologicos y en alimentos puede coexistir, y reaccionar, con azucares y compuestos aminicos, pudiendo contribuir a la reaccion de oscurecimiento no enzimatico de los alimentos (reaccion de maillard), que implica inicialmente a los azucares reductores y los compuestos aminicos. La reactividad del malondialdehido es compleja de entender, ya que este compuesto es inestable en condiciones fisiologicas. El malondialdehido sufre, por un lado, una rapida ruptura hidrolitica que produce acetaldehido, el cual reacciona con el malondialdehido en exceso, formandose 2,4-dihidroximetilen-3-metilglutaraldehido. Por otro lado, el malondialdehido se oligomeriza lentamente a valores de ph proximos a su pk (4.46), formandose el "quasi dimero" e-(3-oxo-1-propen-1-il) malondialdehido, y el "quasi trimero" 2,4-dihidroximetilen-3(2-oxoetil) glutaraldehido. En las reacciones de malondialdehido con amino azucares a ph neutro, se forman como productos mayoritarios enaminales (3-amino-2-propenales), y como productos minoritarios 4-metil-1,4-dihidropiridina-3,5-dicarbaldehidos originados por reaccion de los amino azucares o/y del compuesto aminico producido por escision del amino azucar, con 2,4-dihidroximetilen-3-metilglutaraldehido. En el caso de la 1-amino-1-desoxi-d-fructosa se forma ademas, como producto minoritario, el n,n'-di(1-desoxi-1-fructos-1-il)-1-amino-3-iminopropeno. Los enaminales obtenidos son muy resistentes a la hidrolisis, y aquellos que tienen un grupo carbonilopotencial en el resto de azucar, ciclan al ser calentados, originando los esperados 3-pirrolcarbaldehidos 4- o 5-sustituidos

Nutritional phenolic compounds in red wines determined by HPLC-DAD-ESI-MS and MS/MS technique

Red wine is a rich source of bioactive and nutritional phenolic compounds which show antioxidant properties, present potential health effect, exhibit a free radical scavenging activity as well as a protective activity against arteriosclerosis, coronary heart disease or inhibit the cancer cell growth. In this study, the detailed phenolic profile of Macedonian red wines Vranec, Merlot and Cabernet Sauvignon, was determined. For that purpose, a high-performance liquid chromatography coupled with diode array detector and on line electrospray ionization mass spectrometry (HPLC-DAD-ESI-MS and MS/MS) was used for determination of the individual nutritional phenolic compounds in the wines. For analysis of anthocyanins and other pigments, wines were only diluted with 0.1M HCl (1:4). A solid-phase extraction with Oasis MCX cartridges was applied for separation of flavonols, phenolic acids and stilbenes [1,2]. ESI-MSn analysis were performed in positive ionization mode for identification of anthocyanins, flavonols and flavan-3-ols, and for gallic acid, hydroxycinnamic acid derivatives and stilbenes determination, ESI operated in negative ionization mode [3]. Complex phenolic profile was revealed for all wines composed of anthocyanins, vitisins, hydroxyphenyl-pyranoanthocyanins, flavonols, hydroxycinnamic acid derivatives, flavan-3-ols and stilbenes. Vranec wine was richest in all phenolics, especially anthocyanins that make it deeply colored, fresh and stable, appropriate for production of high quality red wines [4]

Characterization of Merlot wines based on phenolic composition determined by HPLC-DAD-ESI-MS and MS/MS technique

The concentration of phenolic compounds in wine depends on many factors, such as the variety, climate, soil, oenological practices applied for winemaking, aging and storage conditions. The purpose of this investigation was to determine the detailed phenolic profile of Merlot wines (vintage 2008), produced in Tikveš wine region in Republic of N. Macedonia. High-performance liquid chromatography with diode array detection coupled to mass spectrometry (HPLC-DAD-ESI-MS/MS) was used to identify and quantify the phenolic compounds in wines. Identification of the individual phenolic compounds was carried out by comparison of their UV/Vis spectra and retention times with those of the available standards, as well as by comparing the ESI-MS and MS/MS data with the standards analyzed under the same experimental conditions and those found in the literature. Different families of phenolic compounds were considered: anthocyanins, vitisins, hydroxyphenyl-pyranoanthocyanins, flavonols, hydroxycinnamic acids derivatives and stilbenes. With regards to pigments, malvidin-3-glucoside and its 3-acetylglucoside and 3-p-coumaroylglucoside derivatives were the major anthocyanins, while vitisin A and 10-DHP-pyranomalvidin-3-glucoside (pinotin A) were the dominant pyranoanthocyanins. Obtained results are significant data for the Macedonian winemaking industry to understand the nature and content of phenolic compounds in Merlot wines, as the most important components that influence the color, stability and sensorial properties of wines

Identification of anthocyanins and anthocyanin derivatives in Vranec wines during aging

This study aimed to characterization of the major anthocyanins (3-monoglucosides, 3-acetylglucosides, and 3-coumaroylglucosides), pyranoanthocyanins and hydroxyphenyl-pyranoanthocyanins in Vranec wines during aging of three years. The HPLC-DAD–ESI-MSn technique was used for identification of the analytes. Anthocyanins presented mass spectra characterized with two signals, molecular ion M+ and fragment ions [M-162]+, [M-204]+ and [M-308]+ which resulted from the loss of glucose, acetylglucose and p-coumaroylglucose groups, respectively. The pyranoanthocyanins derived from pyruvic acid, called 10-carboxy-pyranoanthocyanins or A-type vitisins, such as 10-carboxy-pyranomalvidin-3-glucoside (vitisin A), 10-carboxy-pyranomalvidin-3-acetylglucoside (acetyl-vitisin A) and 10-carboxy-pyranomalvidin-3-p-coumaroylglucoside (p-coumaroyl-vitisin A) were identified according to their molecular ions (M+ ) and the characteristic fragment ([M+H]+ = m/z 399). B-type vitisins, resulting from cycloaddition reaction between anthocyanins and acetaldehyde, including pyranomalvidin-3-glucoside (vitisin B) and pyranomalvidin-3- acetylglucoside (acetyl-vitisin B), presented molecular signals M+ at m/z 517 and 559 and producing a fragment ion at m/z 355 by loss of glucoside (162u) and acetylgucoside (204u) groups, respectively. Moreover, six hydroxyphenyl-pyranoanthocyanins produced in the reaction of caffeic acid (10-(3′′′,4′′′-dihydroxyphenyl)-pyranomalvidin-3-glucoside, 10-(3′′′,4′′′-dihydroxyphenyl)-pyrano malvidin-3-acetylglucoside and 10-(3′′′,4′′′-dihydroxyphenyl)-pyrano malvidin-3-p-coumaroylglucoside) and p-coumaric acid (10-(4′′′-monohydroxyphenyl) derivatives of pyranomalvidin-3-glucoside, pyranomalvidin-3-acetylglucoside and pyranomalvidin-3-p-coumaroylglucoside) with different anthocyanins, were detected in the wines

Phenolic composition of red wines from Republic of Macedonia

Polyphenols are large and complex group of compounds which determine important characteristics, such as colour, mouthfeel, astringency and bitterness, of wine. Furthermore, they are the main responsible components for the differences between red and white wines, especially for the colour, taste, and mouth-feel sensations of red wines. Phenolic compounds are classified as flavonoids, including: anthocyanins; flavan-3-ols (monomers, olygomers and polymers), flavonols and dihydroflavonols, and non-flavonoids: hydroxybenzoic acids and derivatives; hydroxycimmanmic acids and derivatives; and stilbenes. Anthocyanins are the main pigments in red wines, responsible for their colour. Flavan-3-ols as monomers are bitter compounds and the oligomeric and polymeric flavan-3-ols contribute to wine astringency. Grape and red wine are the major dietary sources of stilbenes, considered as phytoalexins whose formation in grapes is correlated to disease resistance. Moreover, phenolic compounds in wine exhibit free radical scavenging activity, as well as, protective activity against arteriosclerosis and coronary heart disease. Phenolic composition of Vitis Vinifera red wines Vranec, Merlot and Cabernet Sauvignon from the Tikveš region in Republic of Macedonia, has been studied using HPLC-DAD-MS and MS/MS techniques. Fifty-two phenolic compounds have been identified and quantified in the wine samples [1]. In all varieties, malvidin-3-glucoside and its derivatives were the major compounds. 10-carboxy-pyranomalvidin-3-glucoside (vitisin A) and 10-p-hydroxyphenyl-pyranomalvidin-3-glucoside were the main compounds from the family of vitisin-like and hydroxyphenyl-like pyranoanthocyanins, respectively. Vranec wine, which has intensive dark red and ruby colour, presented highest phenolics content having highest concentration of anthocyanins, vitisins, hydroxyphenyl-pyranoanthocyanins, flavonols, hydroxycinnamic acid derivatives and stilbenes in comparison to the other varieties studied, followed by Merlot and Cabernet Sauvignon [2,3]

Free amino acid composition and botanical origin of honey

The main amino acids found in 31 Spanish honeys of five different single botanical origins, were proline, phenylalanine, tyrosine and lysine, followed by arginine, glutamic acid, histidine and valine. Principal component analysis explained 64% of the variance with the first three PC variables, the lavender honeys being the only group well differentiated. Although the best grouped honeys were those from orange blossom, overlapping with eucalyptus honeys, on the one hand, and with the indistinguishable group formed by rosemary and thyme honeys, on the other hand, was observed. The Student–Newman–Keuls test allowed the grouping of rosemary, thyme and orange blossom honeys, whereas eucalyptus and lavender honeys showed specific amino acid compositions which made them different when compared with this group and also between themselves. Lavender honeys had the highest concentrations of tyrosine. The results obtained for the former honeys together with those obtained for another set of 17 samples, were used to establish a range for amino acid composition of Spanish honeys.The authors wish to thank the Instituto Nacional de Investigaciones Agrarias (I.N.I.A.) for financial support (Projects API-004-C21 and API99-004).Peer reviewe