Antioxidant properties of roasted coffee residues

The antioxidant activity of roasted coffee residues was evaluated. Extraction with four solvents (water, methanol, ethanol, and n-hexane) showed that water extracts of roasted coffee residues (WERCR) produced higher yields and gave better protection for lipid peroxidation. WERCR showed a remarkable protective effect on oxidative damage of protein. In addition, WERCR showed scavenging of free radicals as well as the reducing ability and to bind ferrous ions, indicating that WERCR acts as both primary and secondary antioxidants. The HPLC analyses showed that phenolic acids (chlorogenic acid and caffeic acid) and nonphenolic compounds [caffeine, trigonelline, nicotinic acid, and 5-(hydroxymethyl)furfuraldehyde] remained in roasted coffee residues. These compounds showed a protective effect on a liposome model system. The concentrations of flavonoids and polyphenolic compounds in roasted coffee residues were 8,400 and 20,400 ppm, respectively. In addition, the Maillard reaction products (MRPs) remaining in roasted coffee residues were believed to show antioxidant activity. These data indicate that roasted coffee residues have excellent potential for use as a natural antioxidant source because the antioxidant compounds remained in roasted coffee residues.     

The antioxidant and chlorogenic acid profiles of whole coffee fruits are influenced by the extraction procedures

Commercial whole coffee fruit extracts and powder samples were analyzed for chlorogenic acids (CGA), caffeine and antioxidant activities. CGA and caffeine were characterized by LC-MS(n) and HPLC accordingly, and quantified by UV absorbance. ORAC, HORAC, NORAC, SORAC and SOAC (antioxidant capacities) were assessed. Three caffeoylquinic acids, three feruloylquinic acids, three dicaffeoylquinic acids, one p-coumaroylquinic acid, two caffeoylferuloylquinic acids and three putative chlorogenic lactones were quantified, along with a methyl ester of 5-caffeoylquinic acid (detected in one sample, the first such report in any coffee material). Multistep whole coffee fruit extracts displayed higher CGA content than single-step extracts, freeze-dried, or air-dried whole raw fruits. Caffeine in multistep extracts was lower than in the single-step extracts and powders. Antioxidant activity in whole coffee fruit extracts was up to 25-fold higher than in powders dependent upon the radical. Total antioxidant activity of samples displayed strong correlation to CGA content.     

Isolation, identification, and quantification of roasted coffee antibacterial compounds

Coffee brew is a widely consumed beverage with multiple biological activities due both to naturally occurring components and to the hundreds of chemicals that are formed during the roasting process. Roasted coffee extract possesses antibacterial activity against a wide range of microorganisms, including Staphylococcus aureus and Streptococcus mutans, whereas green coffee extract exhibits no such activity. The naturally occurring coffee compounds, such as chlorogenic acids and caffeine, cannot therefore be responsible for the significant antibacterial activity exerted by coffee beverages against both bacteria. The very low minimum inhibitory concentration (MIC) found for standard glyoxal, methylglyoxal, and diacetyl compounds formed during the roasting process points to these alpha-dicarbonyl compounds as the main agents responsible for the antibacterial activity of brewed coffee against Sa. aureus and St. mutans. However, their low concentrations determined in the beverage account for only 50% of its antibacterial activity. The addition of caffeine, which has weak intrinsic antibacterial activity, to a mixture of alpha-dicarbonyl compounds at the concentrations found in coffee demonstrated that caffeine synergistically enhances the antibacterial activity of alpha-dicarbonyl compounds and that glyoxal, methylglyoxal, and diacetyl in the presence of caffeine account for the whole antibacterial activity of roasted coffee.     

Interactions between volatile and nonvolatile coffee components. 1. Screening of nonvolatile components

This study is the first of two publications that investigate the phenomena of coffee nonvolatiles interacting with coffee volatile compounds. The purpose was to identify which coffee nonvolatile(s) are responsible for the interactions observed between nonvolatile coffee brew constituents and thiols, sulfides, pyrroles, and diketones. The overall interaction of these compounds with coffee brews prepared with green coffee beans roasted at three different roasting levels (light, medium, and dark), purified nonvolatiles, and medium roasted coffee brew fractions (1% solids after 1 or 24 h) was measured using a headspace solid-phase microextraction technique. The dark roasted coffee brew was slightly more reactive toward the selected compounds than the light roasted coffee brew. Selected pure coffee constituents, such as caffeine, trigonelline, arabinogalactans, chlorogenic acid, and caffeic acid, showed few interactions with the coffee volatiles. Upon fractionation of medium roasted coffee brew by solid-phase extraction, dialysis, size exclusion chromatography, or anion exchange chromatography, characterization of each fraction, evaluation of the interactions with the aromas, and correlation between the chemical composition of the fractions and the magnitude of the interactions, the following general conclusions were drawn. (1) Low molecular weight and positively charged melanoidins present significant interactions. (2) Strong correlations were shown between the melanoidin and protein/peptide content, on one hand, and the extent of interactions, on the other hand (R = 0.83-0.98, depending on the volatile compound). (3) Chlorogenic acids and carbohydrates play a secondary role, because only weak correlations with the interactions were found in complex matrixes.     

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.     

Low molecular weight melanoidins in coffee brew

Analysis of low molecular weight (LMw) coffee brew melanoidins is challenging due to the presence of many non-melanoidin components that complicate analysis. This study focused on the isolation of LMw coffee brew melanoidins by separation of melanoidins from non-melanoidin components that are present in LMw coffee brew material. LMw coffee fractions differing in polarity were obtained by reversed-phase solid phase extraction and their melanoidin, sugar, nitrogen, caffeine, trigonelline, 5-caffeoylquinic acid, quinic acid, caffeic acid, and phenolic groups contents were determined. The sugar composition, the charge properties, and the absorbance at various wavelengths were investigated as well. The majority of the LMw melanoidins were found to have an apolar character, whereas most non-melanoidins have a polar character. The three isolated melanoidin-rich fractions represented 56% of the LMw coffee melanoidins and were free from non-melanoidin components. Spectroscopic analysis revealed that the melanoidins isolated showed similar features as high molecular weight coffee melanoidins. All three melanoidin fractions contained approximately 3% nitrogen, indicating the presence of incorporated amino acids or proteins. Surprisingly, glucose was the main sugar present in these melanoidins, and it was reasoned that sucrose is the most likely source for this glucose within the melanoidin structure. It was also found that LMw melanoidins exposed a negative charge, and this negative charge was inversely proportional to the apolar character of the melanoidins. Phenolic group levels as high as 47% were found, which could be explained by the incorporation of chlorogenic acids in these melanoidins.     

Flavoring components of raw monsooned arabica coffee and their changes during radiation processing

Volatile aroma principles, nonvolatile taste constituents (caffeine and chlorogenic and caffeic acids), and glycosidically bound aroma compounds of monsooned and nonmonsooned raw arabica coffee were analyzed using gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC). Among the most potent odor active constituents known to contribute to the aroma of the green beans, 3-isopropyl-2-methoxypyrazine, 3-isobutyl-2-methoxypyrazine, 4-vinylguaiacol, beta-damascenone, (E)-2-nonenal, trans,trans-2,4-decadienal, phenylacetaldehyde, and 3-methylbutyric acid were detected by GC-MS in both samples. A decrease in content of methoxypyrazines and an increase in 4-vinylguaiacol and isoeugenol resulted in a dominant spicy note of monsooned coffee. These phenolic compounds exist partly as their glycosides, and their release from the bound precursors during monsooning accounted for their higher content in monsooned coffee. A considerable decrease in astringent chlorogenic acid as a consequence of hydrolysis to bitter caffeic acid was noted in monsooned coffee. Radiation processing of nonmonsooned beans at a dose of 5 kGy resulted in an increased rate of monsooning. At this dose a quantitative increase in most of the aroma active components could be observed in all samples studied. Hydrolysis of chlorogenic acid to caffeic acid was noted in radiation-processed monsooned coffee beans irrespective of whether the treatment was carried out before or after monsooning. These changes were, however, not observed in irradiated, nonmonsooned coffee beans, suggesting an enzymatic rather than a radiolytic cleavage of chlorogenic acid. A rationale behind the mechanism of monsooning and radiation-induced enhancement of the monsooning process is discussed.     

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.     

Coffee components inhibit amyloid formation of human islet amyloid polypeptide in vitro: possible link between coffee consumption and diabetes mellitus

Global epidemic studies have suggested that coffee consumption is reversely correlated with the incidence of type 2 diabetes mellitus (T2DM), a metabolic disease. The misfolding of human islet amyloid polypeptide (hIAPP) is regarded as one of the causative factors of T2DM. Coffee extracts have three major active components: caffeine, caffeic acid (CA), and chlorogenic acid (CGA). In this study, the effects of these major coffee components, as well as dihydrocaffeic acid (DHCA) (a major metabolite of CGA and CA), on the amyloidogenicity of hIAPP were investigated by thioflavin-T based fluorescence emission, transmission electronic microscopy, circular dichroism, light-induced cross-linking, dynamic light scattering, and MTT-based cell viability assays. The results suggest that all components show varied inhibitory effects on the formation of toxic hIAPP amyloids, in which CA shows the highest potency in delaying the conformational transition of the hIAPP molecule with the most prolonged lag time, whereas caffeine shows the lowest potency. At a 5-fold excess molar ratio of compound to hIAPP, all coffee-derived compounds affect the secondary structures of incubated hIAPP as suggested by the circular dichroism spectra and CDPro deconvolution analysis. Further photoinduced cross-linking based oligomerization and dynamic light scattering studies suggested CA and CGA significantly suppressed the formation of hIAPP oligomers, whereas caffeine showed no significant effect on oligomerization. Cell protection effects were also observed for all three compounds, with the protection efficiency being greatest for CA and least for CGA. These findings suggest that the beneficial effects of coffee consumption on T2DM may be partly due to the ability of the major coffee components and metabolites to inhibit the toxic aggregation of hIAPP.     

Roasting process of coffee beans as studied by nuclear magnetic resonance: time course of changes in composition

In this paper, we report a (1)H and (13)C nuclear magnetic resonance (NMR)-based comprehensive analysis of coffee bean extracts of different degrees of roast. The roasting process of coffee bean extracts was chemically characterized using detailed signal assignment information coupled with multivariate data analysis. A total of 30 NMR-visible components of coffee bean extracts were monitored simultaneously as a function of the roasting duration. During roasting, components such as sucrose and chlorogenic acids were degraded and components such as quinic acids, N-methylpyridinium, and water-soluble polysaccharides were formed. Caffeine and myo-inositol were relatively thermally stable. Multivariate data analysis indicated that some components such as sucrose, chlorogenic acids, quinic acids, and polysaccharides could serve as chemical markers during coffee bean roasting. The present composition-based quality analysis provides an excellent holistic method and suggests useful chemical markers to control and characterize the coffee-roasting process.     

Espresso coffee residues: a valuable source of unextracted compounds

Espresso spent coffee grounds were chemically characterized to predict their potential, as a source of bioactive compounds, by comparison with the ones from the soluble coffee industry. Sampling included a total of 50 samples from 14 trademarks, collected in several coffee shops and prepared with distinct coffee machines. A high compositional variability was verified, particularly with regard to such water-soluble components as caffeine, total chlorogenic acids (CGA), and minerals, supported by strong positive correlations with total soluble solids retained. This is a direct consequence of the reduced extraction efficiency during espresso coffee preparation, leaving a significant pool of bioactivity retained in the extracted grounds. Besides the lipid (12.5%) and nitrogen (2.3%) contents, similar to those of industrial coffee residues, the CGA content (478.9 mg/100 g), for its antioxidant capacity, and its caffeine content (452.6 mg/100 g), due to its extensive use in the food and pharmaceutical industries, justify the selective assembly of this residue for subsequent use.     

Screening of raw coffee for thiol binding site precursors using "in bean" model roasting experiments

The purpose of the following study was to investigate the influence of coffee roasting on the thiol-binding activity of coffee beverages, and to investigate the potential of various green bean compounds as precursors of thiol-binding sites by using promising "in bean" model roast experiments. Headspace gas chromatographic analysis on coffee brews incubated in the presence of the roasty-sulfury smelling 2-furfurylthiol for 20 min at 30 degrees C in septum-closed vessels revealed that the amounts of "free" thiol decreased drastically with increasing the roasting degree of the beans used for preparation of the brews. A half-maximal binding capacity (BC(50)) of 183 mg of 2-furfurylthiol per liter of standard coffee beverage was determined for a roasted coffee (CTN value of 67), thus demonstrating that enormous amounts of the odor-active thiol are "bound" by the coffee. Furthermore, biomimetic "in bean" precursor experiments have been performed in order to elucidate the precursor for the thiol-binding sites in the raw coffee bean. These experiments opened the possibility of studying coffee model reactions under quasi-natural roasting conditions and undoubtedly identified chlorogenic acids as well as thermal degradation products caffeic acid and quinic acid as important precursors for low-molecular-weight thiol-binding sites. In particular, when roasted in the presence of transition metal ions, chlorogenic acids and even more caffeic acid showed thiol-binding activity which was comparable to the activity measured for the authentic coffee brew.     

Caffeine and resistance of coffee to the berry borer Hypothenemus hampei (Coleoptera: Scolytidae)

The role of caffeine as a chemical defense of coffee against the berry borer Hypothenemus hampei was investigated. No positive correlation was observed between resistance and caffeine content in experiments in which seeds from several coffee species presenting genetic variability for the alkaloid were exposed to adult insects. The same was observed in an experiment with coffee seeds that had their caffeine content doubled by imbibition with caffeine aqueous solutions. Other experiments showed that the attractiveness to insects was not related to the caffeine content of mature fruits. These results indicate that H. hampei has evolved an adaptation to handle the toxic effects of caffeine.     

Discriminate analysis of roasted coffee varieties for trigonelline, nicotinic acid, and caffeine content

Arabica and robusta roasted coffees from several geographical origins, in a total of 29 samples, were characterized for their contents in caffeine, trigonelline, and nicotinic acid by a recently developed HPLC/diode-array detector method. All samples were subjected to the same roasting procedure in order to eliminate the variations due to this process. Characterization was achieved by applying multivariate and nonparametric analysis to the chromatographic results. The two coffee varieties were clearly separated by their trigonelline and caffeine contents. Nicotinic acid could not be used as a variety discriminate factor. There was no association with the geographical origin of the samples.     

Phenolic compounds from the leaf extract of artichoke (Cynara scolymus L.) and their antimicrobial activities

A preliminary antimicrobial disk assay of chloroform, ethyl acetate, and n-butanol extracts of artichoke (Cynara scolymus L.) leaf extracts showed that the n-butanol fraction exhibited the most significant antimicrobial activities against seven bacteria species, four yeasts, and four molds. Eight phenolic compounds were isolated from the n-butanol soluble fraction of artichoke leaf extracts. On the basis of high-performance liquid chromatography/electrospray ionization mass spectrometry, tandem mass spectrometry, and nuclear magnetic resonance techniques, the structures of the isolated compounds were determined as the four caffeoylquinic acid derivatives, chlorogenic acid (1), cynarin (2), 3,5-di-O-caffeoylquinic acid (3), and 4,5-di-O-caffeoylquinic acid (4), and the four flavonoids, luteolin-7-rutinoside (5), cynaroside (6), apigenin-7-rutinoside (7), and apigenin-7-O-beta-D-glucopyranoside (8), respectively. The isolated compounds were examined for their antimicrobial activities on the above microorganisms, indicating that all eight phenolic compounds showed activity against most of the tested organisms. Among them, chlorogenic acid, cynarin, luteolin-7-rutinoside, and cynaroside exhibited a relatively higher activity than other compounds; in addition, they were more effective against fungi than bacteria. The minimum inhibitory concentrations of these compounds were between 50 and 200 microg/mL.     

Antiadhesive effect of green and roasted coffee on Streptococcus mutans' adhesive properties on saliva-coated hydroxyapatite beads

Green and roasted coffees of the two most used species, Coffea arabica and Coffea robusta, several commercial coffee samples, and known coffee components were analyzed for their ability to interfere with Streptococcus mutans' sucrose-independent adsorption to saliva-coated hydroxyapatite (HA) beads. All coffee solutions showed high antiadhesive properties. The inhibition of S. mutans' adsorption to HA beads was observed both when coffee was present in the adsorption mixture and when it was used to pretreat the beads, suggesting that coffee active molecules may adsorb to a host surface, preventing the tooth receptor from interacting with any bacterial adhesions. Among the known tested coffee components, trigonelline and nicotinic and chlorogenic acids have been shown to be very active. Dialysis separation of roasted coffee components also showed that a coffee component fraction with 1000 Da < MW < 3500 Da, commonly considered as low MW coffee melanoidins, may sensibly contribute to the roasted coffee's antiadhesive properties. The obtained results showed that all coffee solutions have antiadhesive properties, which are due to both naturally occurring and roasting-induced molecules.     

Evolution of green coffee protein profiles with maturation and relationship to coffee cup quality

Coffee flavor is the product of a complex chain of chemical transformations. The green bean has only a faint odor that is not at all reminiscent of coffee aroma. It contains, however, all of the necessary precursors to generate the unmistakable coffee flavor during roasting. The levels and biochemical status of these precursors may vary in relation to genetic traits, environmental factors, maturation level, postharvest treatment, and storage. To improve our understanding of coffee flavor generation, the sensory and biochemical impact of maturation was assessed. Maturation clearly favored the development of high-quality flavor in the coffee brew. A specific subclass of green coffee beans, however, generated high-quality coffee flavor irrespective of maturation. Biochemical aspects were examined using a dynamic system: immature and mature green coffee suspensions were incubated under air or argon. On the analytical side, a specific pool of flavor precursors was monitored: chlorogenic acids, green coffee proteins, and free amino acids. A link between maturation, the redox behavior of green coffee suspensions, and their sensory scores was identified. Compared to ripe beans, unripe beans were found to be more sensitive to oxidation of chlorogenic acids. Aerobic incubation also triggered the fragmentation or digestion of the 11S seed storage protein and the release of free amino acids.     

Influence of coffee roasting on the incorporation of phenolic compounds into melanoidins and their relationship with antioxidant activity of the brew

In the present study, the influence of coffee roasting on free and melanoidin-bound phenolic compounds and their relationship with the brews' antioxidant activity (AA), evaluated by TRAP, TEAC, and TRAP, were investigated. Changes in the relative content of free chlorogenic acids (CGA), free lactones, and melanoidin-bound phenolic acids during roasting indicate that phenolic compounds were incorporated into melanoidins mainly at early stages of the process, being thereafter partly oxidized to dihydrocaffeic acid, and degraded. Although less than 1% of CGA in green coffee was incorporated into melanoidins during roasting, the relative content of melanoidin-bound phenolic acids increased significantly during this process, reaching up to 29% of total phenolic compounds in brews from dark roasted coffees. Regardless of the AA assay used and considering all roasting degrees, the overall contribution of CGA to the AA of the whole brews was higher than that of melanoidin-bound phenolic compounds. It was estimated that the latter compounds contributed to 25-47% of the AA, depending on the assay used.     

In vitro antioxidant activity of coffee compounds and their metabolites

In this paper we report the antioxidant activity of different compounds which are present in coffee or are produced as a result of the metabolism of this beverage. In vitro methods such as the ABTS*+ [ABTS = 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)] decolorization assay and the oxygen radical absorbance capacity assay (ORAC) were used to assess the capacity of coffee compounds to scavenge free radicals. The importance of caffeine metabolites and colonic metabolites in the overall antioxidant activity associated with coffee consumption is shown. Colonic metabolites such as m-coumaric acid and dihydroferulic acid showed high antioxidant activity. The ability of these compounds to protect human low-density lipoprotein (LDL) oxidation by copper and 2,2'-azobis(2-amidinopropane) dihydrochloride was also explored. 1-Methyluric acid was particularly effective at inhibiting LDL oxidative modification. Different experiments showed that this caffeine metabolite is not incorporated into LDL particles. However, at physiologically relevant concentrations, it was able to delay for more than 13 h LDL oxidation by copper.     

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.