Evaluation of the effect of processing on cocoa polyphenols: antiradical activity,anthocyanins and procyanidins profiling from raw beans to chocolate

The content and composition of anthocyanins and procyanidins in fermented cocoa beans (from different geographic origins: Ecuador, Cameroon, Ivory Coast, Ghana and Nigeria), roasted nibs, cocoa mass and chocolate were determined, beside the determination of the total antiradical capacity. Concerning geographic origin, cocoa beans and processed products from Ecuador showed the highest levels of anthocyanins, followed by Nigeria and Cameroon. Generally, as cocoa beans were further processed, the levels of anthocyanins and flavan‐3‐ols decreased. The largest observed losses of phenolics occurred during roasting. A progressive decreasing trend in polyphenol concentration was observed in the other processed samples as well. Despite the original content of polyphenols in raw cocoa beans, technological processes imply a significant impact on cocoa quality, confirming the need of specific optimisation to obtain high value chocolate.     

Anthocyanin composition of the red wine Babić affected by maceration treatment

Identification of anthocyanins in the wine made of the Croatian autochthonous grape variety of Babić (Vitis vinifera L.) was carried out and their profile was determined by means of high-performance liquid chromatography with diode array and mass spectrometric detection. Dependence of anthocyanins content and profile on maceration treatment conditions was investigated. Statistically significant differences of anthocyanins concentration in wines Babić produced by various maceration treatments were confirmed by the use of multivariate analysis of variances. The investigation results indicated that the maceration temperature exerts higher influence on anthocyanins concentration than the duration of maceration. In addition, on the basis of anthocyanin composition and using different multivariate statistical analyses, differentiation of wines Babić according to maceration treatments was procured.     

Semi-batch extraction of anthocyanins from red grape pomace in packed beds: experimental results and process modelling

A semi-batch extraction process of anthocyanins was studied in a packed bed. Methanol was used as solvent and the raw material studied consisted of skins of the tempranillo grape, which was obtained from the pomace from red wine vinification. The results show large diffusional effects due to strong control from the mass transfer. The best results were obtained using a high temperature and a high flow rate. A penetration model is proposed in terms of a bed of spherical particles. The model provides a value for the diffusion coefficient of the solute within the solid matrix. It can be seen that the adjustment of the model is satisfactory and that it is able to predict, to a reasonable extent, the yield of the extraction process.     

The distribution of anthocyanins in grape skin extracts of port wine cultivars as determined by high performance liquid chromatography

The distribution of anthocyanins in methanolic skin extracts of 16 grape cultivars used for port wine production and grown at five sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Results are confined to the seven most readily separated and identified anthocyanins and are expressed as percentages of their total (88–99% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated. Of these, Mv 3-glucoside was the major pigment (33–60%), being exceeded by Mv 3-p-coumarylglucoside (2–51%) in only two cultivars; Mv 3-acetylglucoside (1–15%) was consistently the lowest. Peonidin 3-glucoside (1–27%) was prominent in four cultivars, but delphinidin 3-glucoside (1–11%), petunidin 3-glucoside (2–11%) and cyanidin 3-glucoside (trace-6%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site, and a useful aid to identification of grape cultivars. The coloured pulp of some cultivars contained peonidin 3-glucoside as a major component, present in greater proportions than in the skin; the percentage of Mv 3-p-coumarylglucoside was lower in pulp than in skin. The identities of six of the seven anthocyanins were confirmed by fast atom bombardment mass spectrometry and the structures of the Mv derivatives were determined by nuclear magnetic resonance. The formation of formyl and acetyl anthocyanin artefacts is described.     

In vitro gastrointestinal digestion of polyphenols from different molasses (pekmez) and leather (pestil) varieties

In this study, to evaluate the in vitro bioaccessibility of eight different pekmez and pestil samples, total phenolics, flavonoids, proanthocyanidins, anthocyanins and antioxidant capacity were determined at different phases of simulated gastrointestinal (GI) digestion. For the analysis of antioxidant activity, four different methods were used including 2,2‐azinobis(3‐ethylbenzothiazoline)‐6‐sulfonic acid, 1,1‐diphenyl‐2‐picrylhydrazil, ferric reducing antioxidant power and cupric ion reducing antioxidant capacity. The results revealed that the dialysed fraction (IN) represented 12–50%, 3–17% and 3–72% of the total phenolics, flavonoids and proanthocyanidins, respectively. Moreover, total antioxidant capacity of IN fraction was 2–57% of the initial values obtained for pekmez and pestil samples. To identify the influence of simulated in vitro GI digestion on total anthocyanins, only black mulberry molasses (pekmez) and plum leather (pestil) were analysed and according to the results no anthocyanins were detected in the IN fraction for both samples. The present study presented a detailed insight of bioaccessibility of polyphenols in various pekmez and pestil samples.     

Rapid determination of free anthocyanins in foodstuffs using high performance liquid chromatography

Anthocyanins constitute a major group of natural pigments, and they are responsible for the colours of fruits and vegetables. A rapid and feasible assay procedure for the determination of free forms of the six most abundant anthocyanins in foods is described. The 3-glucoside forms of pelargonidin, cyanidin, peonidin, delphinidin, petunidin and malvidin with the aglycone cyanidin (as internal standard) were separated by gradient elution and quantified using HPLC-DAD within 18 min. A fast sample preparation step was employed which allows direct injection of samples to the chromatograph without need of chemical extraction. Testing on 28 different vegetable, fruit and processed commercial product samples demonstrated applicability in the concentration range of about 80–420 ng/mL with an accuracy of 99.2 ± 0.2% and an average precision of 0.8%. The method was suggested as a cheap and robust alternative to the previous ones that employ multi-step sample treatment protocols.     

Grape seed removal: effect on phenolics,chromatic and organoleptic characteristics of red wine

Winemakers are interested in wines with low bitterness and astringency, and therefore, there is a preference for a higher presence of skin proanthocyanidins in wines. However, the information regarding the effect of reducing or eliminating seed proanthocyanidins from the must or fermenting wine on the characteristics of finished wines is scarce. For this reason, we elaborated a wine using Monastrell grapes from which the seeds had been removed and compared it with a control wine (CW) made from intact grapes. The anthocyanin and proanthocyanidin concentration and profile, and the chromatic and sensory characteristics were studied. The absence of seed proanthocyanidins did not affect anthocyanin concentration, although the proanthocyanidin concentration was 40% lower than in the CW. The copigmentation (CA) study showed that both wines had a similar extent of CA phenomena although colour intensity was higher when seed proanthocyanidins were present. The panellist evaluated the wines elaborated without seeds as being fruitier, less astringent and with an overall higher quality.     

Enhancement of phenolic compounds content and antioxidant activity of strawberry (Fragaria × ananassa) juice by block freeze concentration technology

The aim of this study was to evaluate the effects of freeze concentration of strawberry juice on content of total phenolic, anthocyanins content and antioxidant activity of the concentrated fluid and the ice obtained. An increase in the values of phenolic content was observed in the concentrate fraction for all the freeze concentration stages (five stages). The process efficiency presented a reduction when compared with the first stage, and however, the average efficiency remained around 65% in all the stages. The concentration of pelargonidin‐3‐O‐glycoside present in samples was increased in all stages. Furthermore, the antioxidant activity of the concentrated fluid of each stage, measured by DPPH and ABTS methods, was significantly higher in comparison with the juice feed. Also, antioxidant activity can be correlated with the content of pelargonidin‐3‐O‐glycoside presented in the strawberry juice. Freeze concentration can be considered a good alternative for improving the antioxidant activity of strawberry juice.     

Combination of a deep eutectic solvent and macroporous resin for green recovery of anthocyanins from Nitraria tangutorun Bobr. fruit

ABSTRACT

This study aimed at extracting and separating anthocyanins from Nitraria tangutorun Bobr. fruit using deep eutectic solvent (DES) combined with macroporous resins. Choline chloride/1,2-propanediol (ChCl-Prop)-based DESs produced higher extraction yields of total anthocyanins from N. tangutorun fruit than pure water and ethanol/methanol/acetone aqueous solutions did, and LX-32 macroporous resin was used to separate total anthocyanins from the DES (recovery＞95%). Additionally, a green and efficient HPLC-DAD method was used for the analysis of total anthocyanins using ethanol and a tartaric acid aqueous solution as mobile phases, and 13 anthocyanins were identified from N. tangutorun fruit using a UPLC-Q-TOF-MS method.

Abbreviations: DES, deep eutectic solvent; ChCl-Prop, choline chloride/1,2-propanediol.     

Bathochromic and stabilising effects of sugar beet pectin and an isolated pectic fraction on anthocyanins exhibiting pyrogallol and catechol moieties

The formation of anthocyanin–metal chelates, exhibiting intense blue colours was monitored over a period up to 10 weeks. Evaluating normalised absorption spectra in the range of 580–700 nm and their proportion of the total area under the curve (AUC), provided information about the blue colour hue, intensity and stability. Colour stability in model solutions containing commercial sugar beet pectin or an isolated pectic polysaccharide fraction (PPF) therefrom, both being naturally enriched in aluminium and ferric ions, was assessed in a pH range of 3.6–7.0. The pectic structures stabilised anthocyanin–metal chelates, and thus blue colours by efficiently preventing complex precipitation. Highest bathochromic shifts and most intense blue colours were observed in PPF model solutions containing delphinidin-3-glucoside (Dpd-3-glc), exhibiting a pyrogallol moiety in the flavylium B-ring, compared to cyanidin- (Cyd-3-glc) and petunidin-3-glucoside (Pet-3-glc), both carrying a catechol substituted B-ring. Hue and intensity of the blue colour at pH 5.0 were only insignificantly influenced by the buffer system except for citrate and phosphate buffers, which both annihilated anthocyanin–metal chelate formation. The blue colours faded following first order kinetics. Best stabilities as deduced from storage experiments performed at 20 ± 2 °C in the dark were observed for Dpd-3-glc. In contrast, Cyd-3-glc displayed shortened half-life values, whereas blue Pet-3-glc chelates decomposed rapidly. These results demonstrate that the solubilisation of anthocyanin–metal chelates by pectic structures is a promising option for developing water soluble natural blue food colourants.