Model studies on the influence of coffee melanoidins on flavor volatiles of coffee beverages

Addition of the total melanoidin fraction isolated by water extraction from medium-roasted coffee powder to a model solution containing a set of 25 aroma compounds mimicking the aroma of a coffee brew reduced, in particular, the intensity of the roasty, sulfury aroma quality. Model studies performed by static headspace analysis revealed that especially three well-known coffee odorants, that is, 2-furfurylthiol (FFT), 3-methyl-2-butene-1-thiol, and 3-mercapto-3-methylbutyl formate, were significantly reduced in the headspace above an aqueous model solution when melanoidins were added. In particular, the low molecular weight melanoidins (1500-3000 Da) led to the most significant decrease in FFT. In contrast, for example, aldehydes remained unaffected by melanoidin addition.     

Quantitation of volatiles and nonvolatile acids in an extract from coffee beverages: correlation with antioxidant activity

The antioxidant activities of a commercial brewed coffee were investigated by measuring malonaldehyde (MA) formation from oxidized cod liver oil using a gas chromatographic method (MA-GC assay) and a thiobarbituric acid method (TBA assay). The highest antioxidant activity obtained by the MA-GC assay was from regular whole brewed coffee (97.8%) at a level of 20%, and the highest antioxidant activity obtained by the TBA assay was from decaffeinated whole brewed coffee (96.6%) at a level of 5%. Among 31 chemicals identified in a dichloromethane extract, guaiacol, ethylguaiacol, and vinylguaiacol exhibited antioxidant activities, which were comparable to that of alpha-tocopherol. Among nine chlorogenic acids (three caffeoylquinic acids, three feruloylquinic acids, and three dicaffeoylquinic acids) identified, 5-caffeoylquinic acid contained the greatest amount both in regular (883.5 microg/mL) and in decaffeinated (1032.6 microg/mL) coffees; it exhibited 24.5% activity by the MA-GC assay and 45.3% activity by the TBA assay at a level of 10 microg/mL. Caffeic and ferulic acids showed moderate antioxidant activities in both assays.     

Changes in headspace volatile concentrations of coffee brews caused by the roasting process and the brewing procedure

Headspace-solid-phase microextraction technique (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry (GC-O) were used to characterize the aroma compounds of coffee brews from commercial conventional and torrefacto roasted coffee prepared by filter coffeemaker and espresso machine. A total of 47 volatile compounds were identified and quantified. Principal component analysis (PCA) was applied to differentiate coffee brew samples by volatile compounds. Conventional and torrefacto roasted coffee brews were separated successfully by principal component 1 (68.5% of variance), and filter and espresso ones were separated by principal component 2 (19.5% of variance). By GC olfactometry, a total of 34 aroma compounds have been perceived at least in half of the coffee extracts and among them 28 were identified, among which octanal was identified for the first time as a contributor to coffee brew aroma.     

Correlation between some nutritional components and the total antioxidant capacity measured with six different assays in eight horticultural crops

The contents of antioxidant nutritional compounds, total soluble phenolics (TSP), vitamin C, vitamin E, beta-carotene, and total carotenoids (TC), were correlated with the total antioxidant capacity (AOC) of hydrophilic (HPE) and lipophilic extracts (LPE) from eight horticultural crops, namely, guava, avocado, black sapote, mango, papaya, prickly pear fruit, cladodes, and strawberry. AOC was measured using six different assays: 2,2'-diphenyl-1-picrylhydrazyl (DPPH), N,N-dimethyl-p-phenylendiamine (DMPD), ferric-ion-reducing antioxidant power (FRAP), oxygen radical absorbance capacity (ORAC), Trolox equivalent antioxidant capacity (TEAC), and total oxidant scavenging capacity (TOSC). AOC values from HPE were about 95 times higher than LPE values. HPE of guava had the highest AOC value when evaluated with DMPD, DPPH, FRAP, TEAC, and TOSC assays, whereas with ORAC assay, black sapote had the highest value. HPE of papaya and prickly pear fruit presented the lowest AOC values with all assays. From HPE, vitamin C and TSP contents were highly correlated with AOC for all assays, while from LPE, TC and beta-carotene contents possessed a high correlation with AOC only in the DMPD assay.     

Interactions between flavonoids and proteins: effect on the total antioxidant capacity

Flavonoids are potent antioxidants. It is also known that flavonoids bind to proteins. The effect of the interaction between tea flavonoids and proteins on the antioxidant capacity was examined. Their separate and combined antioxidant capacities were measured with the Trolox equivalent antioxidant capacity (TEAC) assay. It was observed that the antioxidant capacity of several components of green and black tea with alpha-, beta-, and kappa-casein or albumin is not additive; that is, a part of the total antioxidant capacity is masked by the interaction. This masking depends on both the protein and the flavonoid used. Components in green and black tea, which show the highest masking in combination with beta-casein, are epigallocatechin gallate and gallic acid. The results demonstrate that the matrix influences the efficacy of an antioxidant.     

Unravelling the total antioxidant capacity of pinotage wines: contribution of phenolic compounds

The total antioxidant capacity (TAC) and phenolic composition of 139 Pinotage wines (2002 and 2003 vintages) were determined using the 2,2'-azino-di(3-ethylbenzo-thialozine-sulfonic acid) scavenging assay and high-performance liquid chromatography, respectively. The contribution of individually quantified phenolic compounds to the wine TAC was calculated using their concentrations and Trolox equivalent antioxidant capacity (TEAC) values. The TEAC values of quercetin-3-galactoside, isorhamnetin, and peonidin-3-glucoside are reported for the first time. Between 11 and 24% of the measured TAC of Pinotage wines was explained by the sum of the calculated contributions of their quantified phenolic compounds comprising monomeric phenolic compounds and procyanidin B1. Ultrafiltration was carried out to attempt separation of monomeric and polymeric phenolic compounds. Analysis of ultrafiltration permeates and retentates enabled estimation of the TAC contribution of large molecular weight (MW) unknown compounds (46%) (>50 kDa), including oligomeric and polymeric phenolic compounds and small MW unknown compounds (34%) (<50 kDa). Three mixtures, containing 12 phenolic compounds in typical concentrations expected in Pinotage wines, exhibited 16-23% synergistic antioxidant activity. This suggests that synergy between phenolic compounds does play a role in the wine TAC but that it does not explain the large discrepancy between measured and calculated TAC values.     

Evolution of antioxidant capacity during storage of selected fruits and vegetables

Interest in the consumption of fresh fruits and vegetables is, to a large extent, due to its content of bioactive nutrients and their importance as dietary antioxidants. Among all of the selected fruits and vegetables, strawberries and black grapes have relatively high antioxidant capacities associated with high contents of total phenolic compounds, ascorbic acid, and flavonols. More interesting, the results of this study indicated that in most fruits and vegetables storage did not affect negatively the antioxidant capacity. Better, in some cases, an increase of the antioxidant capacity was observed in the days following their purchase, accompanied by an increase in phenolic compounds. In general, fruits and vegetables visually spoil before any significant antioxidant capacity loss occurs except in banana and broccoli. When ascorbic acid or flavonoids (aglycons of flavonols and anthocyanins) were concerned, the conclusions were similar. Their content was generally stable during storage.     

Phenolic constituents and antioxidant capacity of four underutilized fruits from the Amazon region

The Amazon region comprises a plethora of fruit-bearing species of which a large number are still agriculturally unimportant. Because fruit consumption has been attributed to an enhanced physical well-being, interest in the knowledge of the chemical composition of underexplored exotic fruits has increased during recent years. This paper provides a comprehensive identification of the polyphenolic constituents of four underutilized fruits from the Amazon region by HPLC/DAD-ESI-MS(n). Arac?a? ( Psidium guineense ), jambola?o ( Syzygium cumini ), muruci ( Byrsonima crassifolia ), and cutite ( Pouteria macrophylla ) turned out to be primarily good sources of hydrolyzable tannins and/or flavonols. Additionally, different flavanonols and proanthocyanidins were identified in some fruits. The antioxidant capacity was determined by using the total oxidant scavenging capacity (TOSC) assay. Cutite showed the highest antioxidant capacity followed by jambola?o, arac?a?, and muruci.     

Contribution of individual polyphenolics to total antioxidant capacity of plums

To study the effect of polyphenolics on antioxidant capacities of plums, the amounts of total phenolics, total flavonoids and individual phenolic compounds, and vitamin C equivalent antioxidant capacity (VCEAC) of eleven plum cultivars was determined. There was a good linear relationship between the amount of total phenolics and total antioxidant capacity (r2 = 0.9887). The amount of total flavonoids and total antioxidant capacity also showed a good correlation (r2 = 0.9653). Although the summation of individual antioxidant capacity was lower than the total antioxidant capacity of plum samples, there was a positive correlation (r2 = 0.9299) of total antioxidant capacity of plum samples with the sum of the VCEACs calculated from individual phenolics. Chlorogenic acids and glycosides of cyanidin, peonidin, and quercetin were major phenolics among eleven plum cultivars. The antioxidant capacity of chlorogenic acids and anthocyanins showed higher correlation (r2) of 0.7751 and 0.6616 to total VCEAC, respectively, than that of quercetin glycosides (r2 = 0.0279). Chlorogenic acids were a major source of antioxidant activity in plums, and the consumption of one serving (100 g) of plums can provide antioxidants equivalent to 144.4-889.6 mg of vitamin C.     

Contribution of chlorogenic acids to the iron-reducing activity of coffee beverages

The iron-reducing activity of coffee beverages was determined by the ferric reducing antioxidant power (FRAP) assay. The influence on FRAP due to the degree of roasting (light, medium, and dark), species (Coffea arabica and Coffea robusta), and caffeine content (regular and decaffeinated) was investigated using ground and soluble coffee samples. The concentration of specific chlorogenic acids and caffeine in the beverages was determined by high-performance liquid chromatography and related to FRAP using Pearson correlation coefficients. All measurements were expressed per unit of soluble solids. Beverages prepared with ground coffee had, on average, 27% higher FRAP values than those prepared with soluble coffee (p < 0.05). In the former beverages, FRAP of C. robusta samples was significantly higher (on average, 50.3%) when compared to that of C. arabica samples, and FRAP values decreased with increasing degree of roasting (p < 0.05). A strong correlation (r > 0.91) was found between FRAP and the total content of chlorogenic acids, particularly that of the caffeoylquinic acid isomers. The iron-reducing activity of coffee beverages was not influenced by caffeine.     

Headspace GC and sensory analysis characterization of the influence of different milk additives on the flavor release of coffee beverages

Previous investigations of coffee flavor have been confined to the analysis of the aroma substances. These investigations showed that about 30 volatile compounds were substantially responsible for the coffee flavor. The aim of this study was to investigate the influence of different milk additives and one coffee whitener on the release of flavor impact compounds from coffee beverages. For the investigation of these effects an external static headspace technique was developed. With this technique the most potent odorants of the coffee beverage were determined. Analyses were performed by gas chromatography/olfactometry, flame ionization detection, and mass spectrometric detection. In addition, sensory studies of the odor profiles were performed. Milk and vegetable products as additives for coffee beverages affected the release of aroma substances in the brew through their lipid, protein, and carbohydrate components. All beverages with an additive showed reduced, but typical, odor profiles for each additive.     

Major phenolics in apple and their contribution to the total antioxidant capacity

The contribution of each phytochemical to the total antioxidant capacity of apples was determined. Major phenolic phytochemicals of six apple cultivars were identified and quantified, and their contributions to total antioxidant activity of apples were determined using a 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical scavenging assay and expressed as vitamin C equivalent antioxidant capacity (VCEAC). Average concentrations of major phenolics and vitamin C in six apple cultivars were as follows (mg/100 g of fresh weight of apples): quercetin glycosides, 13.20; procyanidin B(2), 9.35; chlorogenic acid, 9.02; epicatechin, 8.65; phloretin glycosides, 5.59; vitamin C, 12.80. A highly linear relationship (r (2) > 0.97) was attained between concentrations and total antioxidant capacity of phenolics and vitamin C. Relative VCEAC values of these compounds were in the order quercetin (3.06) > epicatechin (2.67) > procyanidin B(2) (2.36) > phloretin (1.63) > vitamin C (1.00) > chlorogenic acid (0.97). Therefore, the estimated contribution of major phenolics and vitamin C to the total antioxidant capacity of 100 g of fresh apples is as follows: quercetin (40.39 VCEAC) > epicatechin (23.10) > procyanidin B(2) (22.07) > vitamin C (12.80) > phloretin (9.11) > chlorogenic acid (8.75). These results indicate that flavonoids such as quercetin, epicatechin, and procyanidin B(2) rather than vitamin C contribute significantly to the total antioxidant activity of apples.     

Phenolic constituents, furans, and total antioxidant status of distilled spirits.

The concentrations of 11 phenols and 5 furans were measured in 12 categories of distilled spirits by HPLC methodology, together with the total antioxidant status (TAS) of the same beverages. Ellagic acid was the phenol present in highest concentration in all beverages. Moderate amounts of syringaldehyde, syringic acid, and gallic acid, as well as lesser amounts of vanillin and vanillic acid, were measurable in most samples of whiskey, brandy, and rum but were largely undetectable in gin, vodka, liqueurs, and miscellaneous spirits. 5-(Hydroxymethyl)furfural was the predominant furan in the former three beverages, notably cognac, with 2-furaldehyde the next highest, but these were undetectable in most of the latter beverages. Highest TAS values were given by armagnac, cognac, and bourbon whiskey, all three of which tended toward the highest concentrations of phenols. Negative TAS values were exhibited by rum, vodka, gin, and miscellaneous spirits in line with the low or undetectable phenol concentrations in these beverages. Wood aging is the most likely source of phenols and furans in distilled spirits. Those beverages exposed to this treatment contain significant antioxidant activity, which is between the ranges for white and red wines, with the potential to augment the antiatherosclerotic functions attributable to the ethanol that they contain.     

Comparison of the antioxidant activity of commonly consumed polyphenolic beverages (coffee, cocoa, and tea) prepared per cup serving.

In this study, the in vitro low-density lipoprotein oxidation model was used to assess the relative antioxidant activity of the polyphenolic beverages tea, coffee, and cocoa on a cup-serving basis. The beverages were prepared as 0.7-2.5% soluble coffee and 1.5-3.5% cocoa; teas (green, black, or herbal) were prepared as one tea bag infused over 5 min in 220 mL of hot water. Under these standard cup serving conditions, the antioxidant activity as determined by the lag time was in the range of 292-948 min for coffee, 217-444 min for cocoa, 186-338 min for green tea, 67-277 min for black tea, and 6-78 min for herbal tea. Addition of milk did not alter the antioxidant activity. The influence of coffee bean source and degree of roasting was further investigated. Green coffee beans of Robusta coffee exhibited a 2-fold higher antioxidant activity than Arabica coffee, but after roasting this difference was no longer significant. In conclusion, these commonly consumed beverages have a significant antioxidant activity, the highest being soluble coffee on a cup-serving basis.     

Assessing the antioxidant activity of melanoidins from coffee brews by different antioxidant methods

Antioxidant activity of instant coffees produced from the same green coffee beans roasted at three different degrees was analyzed. Coffee melanoidins were obtained by ultrafiltration (10 kDa cutoff) and subsequent diafiltration. Pure melanoidins were isolated from melanoidins after overnight incubation in 2 M NaCl and then ultrafiltered. Filtrates, corresponding to the low molecular weight (LMW) fraction noncovalently linked to the melanoidin skeleton, were also preserved. Antioxidant activity of coffee brews (CB), melanoidins (M), pure melanoidins (PM), and bounded melanoidin compounds (BMC) were tested using the 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and ferric reducing power (FRAP) methods. The correlation between the different methods was studied. The higher contribution of melanoidins to the total antioxidant activity of coffees was shown to be caused by the LMW compounds linked noncovalently to the melanoidin skeleton, as data from BMC confirmed. CB, M, and BMC fractions exert the highest antioxidant activity in aqueous media, whereas PM was not dependent on the reaction media. The highest correlation was found between DPPH and FRAP methods.     

Effect of roasting on the antioxidant activity of coffee brews

Colombian Arabica coffee beans were roasted to give light, medium, and dark samples. Their aqueous extracts were analyzed by gel filtration chromatography, UV-visible spectrophotometry, capillary electrophoresis, and the ABTS(*)(+) assay. A progressive decrease in antioxidant activity (associated mainly with chlorogenic acids in the green beans) with degree of roasting was observed with the simultaneous generation of high (HMM) and low molecular mass (LMM) compounds possessing antioxidant activity. Maximum antioxidant activity was observed for the medium-roasted coffee; the dark coffee had a lower antioxidant activity despite the increase in color. Analysis of the gel filtration chromatography fractions showed that the LMM fraction made a greater contribution to total antioxidant activity than the HMM components.     

Electrochemical sensing of total antioxidant capacity and polyphenol content in wine samples using amperometry online-coupled with microdialysis

This work describes the method for total antioxidant capacity (TAC) and/or total content of phenolics (TCP) analysis in wines using microdialysis online-coupled with amperometric detection using a carbon microfiber working electrode. The system was tested on 10 selected wine samples, and the results were compared with total reactive antioxidant potential (TRAP), oxygen radical absorbance capacity (ORAC), and chemiluminescent determination of total antioxidant capacity (CL-TAC) methods using Trolox and catechin as standards. Microdialysis online-coupled with amperometric detection gives similar results to the widely used cyclic voltammetry methodology and closely correlates with ORAC and TRAP. The problem of electrode fouling is overcome by the introduction of an electrochemical cleaning step (1-2 min at the potential of 0 V vs Ag/AgCl). Such a procedure is sufficient to fully regenerate the electrode response for both red and white wine samples as well as catechin/Trolox standards. The appropriate size of microdialysis probes enables easy automation of the electrochemical TAC/TCP measurement using 96-well microtitration plates.     

Flavored waters: influence of ingredients on antioxidant capacity and terpenoid profile by HS-SPME/GC-MS

The antioxidant profiles of 39 water samples (29 flavored waters based on 10 natural waters) and 6 flavors used in their formulation (furnished by producers) were determined. Total phenol and flavonoid contents, reducing power, and DPPH radical scavenging activity were the optical techniques implemented and included in the referred profile. Flavor extracts were analyzed by HS-SPME/GC-MS to obtain the qualitative and quantitative profiles of the volatile fraction of essential oils. Results pointed out a higher reducing power (0.14-11.8 mg of gallic acid/L) and radical scavenging activity (0.29-211.5 mg Trolox/L) of flavored waters compared with the corresponding natural ones, an interesting fact concerning human health. Bioactive compounds, such as polyphenols, were present in all samples (0.5-359 mg of gallic acid/L), whereas flavonoids were not present either in flavored waters or in flavors. The major components of flavor extracts were monoterpenes, such as citral, α-limonene, carveol, and α-terpineol.     

Quantitative studies on the formation of phenol/2-furfurylthiol conjugates in coffee beverages toward the understanding of the molecular mechanisms of coffee aroma staling

To gain a more comprehensive knowledge of the contribution of recently identified phenol/thiol conjugates to the storage-induced degradation of odorous thiols, the concentrations of the sulfury-roasty smelling key odorant 2-furfurylthiol and the concentrations of the putative thiol-receptive di- and trihydroxybenzenes pyrogallol (1), hydroxyhydroquinone (2), catechol (3), 4-ethylcatechol (4), 4-methylcatechol (5), and 3-methylcatechol (6), as well as of the phenol/thiol conjugates 3-[(2-furylmethyl)sulfanyl]catechol (7), 3-[(2-furylmethyl)sulfanyl]-5-ethylcatechol (8), 4-[(2-furylmethyl)sulfanyl]hydroxyhydroquinone (9), and 3,4-bis[(2-furylmethyl)sulfanyl]hydroxyhydroquinone (10) were quantitatively determined in fresh and stored coffee beverages by means of stable isotope dilution analyses (SIDA). Although 2 was found to be the quantitatively predominant trihydroxybenzene in freshly prepared coffee brew, this compound exhibited a very high reactivity and decreased rapidly during coffee storage to generate the conjugates 9 and 10. After only 10 min, about 60% of the initial amount of 2-furfurylthiol in a coffee beverage reacted with 2 to give 9 and 10. In contrast, conjugate 7 was found to be exclusively formed during coffee roasting because its initial concentration as well as the amount of its putative precursor, phenol 3, was not affected by storage. It is interesting to note that the concentration of 8 was increased with increasing incubation time, but its putative precursor 4 was not affected, thus indicating another formation pathway most likely via the chlorogenic acid degradation product 4-vinylcatechol. This study demonstrates for the first time that the loss of 2-furfurylthiol during coffee storage is mainly due to the oxidative coupling of the odorant to hydroxyhydroquinone (2), giving rise to the conjugates 9 and 10.     

Unraveling the contribution of melanoidins to the antioxidant activity of coffee brews

Instant coffees produced from the same green coffee beans were supplied from a company in different roasting degrees, light, medium, and dark. Melanoidins were obtained by ultrafiltration (10 kDa) and subsequent diafiltration. Pure melanoidins were isolated from melanoidins after overnight incubation in 2 M NaCl. The antioxidant activities of instant coffees, melanoidins, and pure melanoidins were tested using the conjugated diene formation from a 2,2'-azobis(2-amidinopropane) dihydrochloride-induced linoleic acid oxidation in an aqueous system. No significant differences were found between melanoidins and pure melanoidins with different roasting degrees. Therefore, the contribution of the pure melanoidin fraction to the total antioxidant activity of melanoidins was significantly lower. More than 50% of the antioxidant activity of melanoidins is due to low molecular weight compounds linked non-covalently to the melanoidin skeleton. A new concept of the overall antioxidant properties of food melanoidins is described, where chelating ability toward low molecular weight antioxidant compounds is connected to the stabilization of these compounds involved in the shelf life of the product.