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PubMed2002

Coffee, tea, and caffeine consumption and breast cancer incidence in a cohort of Swedish women.

PURPOSE: Coffee, caffeinated tea, and caffeine have been suggested to play a role in breast carcinogenesis or in the promotion or inhibition of tumor growth. Prior epidemiologic evidence has not supported an overall association between consumption of caffeinated beverages and risk of breast cancer, but consumption in some studies was low. METHODS: We studied this relation in the Swedish Mammography Screening Cohort, a large population-based prospective cohort study in Sweden comprising 59,036 women aged 40-76 years. Sweden has the highest coffee consumption per capita in the world. RESULTS: During 508,267 person-years of follow-up, 1271 cases of invasive breast cancer were diagnosed. Women who reported drinking 4 or more cups of coffee per day had a covariate-adjusted hazard ratio of breast cancer of 0.94 [95% confidence interval (CI) 0.75-1.28] compared to women who reported drinking 1 cup a week or less. The corresponding hazard ratio for tea consumption was 1.13 (95% CI 0.91-1.40). Similarly, women in the highest quintile of self-reported caffeine intake had a hazard ratio of beast cancer of 1.04 (95% CI 0.87-1.24) compared to women in the lowest quintile. CONCLUSIONS: In this large cohort of Swedish women, consumption of coffee, tea, and caffeine was not associated with breast cancer incidence.

Adult↗
PubMed2000

Pitfalls in the toxicological analysis of an isobutyl nitrite-adulterated coffee drink.

A forensic investigation was carried out on one poisoning case, where cyanide was first detected in an evidence sample of a canned coffee drink. A more complete study revealed that it had been adulterated with isobutyl nitrite (IBN) and not cyanide. We examined the detectivity of IBN and related compounds by headspace gas chromatography and capillary electrophoresis. IBN decomposes to isobutyl alcohol (iBuOH) and nitrite in aqueous solution, and under higher temperature and more acidic conditions, the rate of this reaction becomes more rapid. IBN was also produced by the esterification of iBuOH with nitrite below pH 5. Cyanide was produced in a coffee solution by the addition of nitrite below pH 6. An IBN-spiked canned coffee drink solution was stored at 4 degrees C and periodically analyzed for IBN, iBuOH, nitrite, nitrate, and cyanide. Since the IBN level decreased rapidly, iBuOH was produced in an almost 90% molar yield. Nitrite production reached a maximum of 40% molar recovery on the first day and then gradually disappeared. The nitrate level reached a plateau of approximately 60% molar recovery. Cyanide was also detected, and its level at the 14th day was approximately 0.26% molar recovery. These findings suggest that, in a coffee drink solution, IBN undergoes hydrolysis to produce iBuOH and nitric acid, which is oxidized to nitrate and also produces cyanide through the nonspecific oxidation of organic compounds under acidic conditions.

Chromatography, Gas↗
PubMed2001

Effect of roasting conditions on reduction of ochratoxin a in coffee.

A commercial lot of green coffee, naturally contaminated with ochratoxin A (OTA), was roasted under various conditions, and the effects on its final OTA content were determined. Precautions were taken in sampling the coffee to cope with OTA inhomogeneity. The roasting conditions were kept within the range of commercial practice. Roasting time was varied from 2.5 to 10 min, and the roast color varied from light medium to dark. The differences in OTA reduction between the different levels of roasting times and colors did not reach statistical significance. However, for all roasting conditions, the reduction was highly significant, 69% reduction over the combined results. In total, nine studies by various authors about OTA reduction during coffee roasting are now available. Seven out of these nine reported that the relevant range of OTA reductions was between 69 and 96%. Among these seven,are all four studies that reported using naturally contaminated beans, a sampling procedure adapted to mycotoxin inhomogeneity, and roasting conditions within the range of actual practice. Three different explanations are available for this reduction: physical removal of OTA with chaff, isomerization at the C-3 position into another diastereomer, and thermal degradation with possible involvement of moisture. All three explanations may play a partial role in the OTA reduction during coffee roasting.

Coffee↗
PubMed2002

Rapid, low cost thin-layer chromatographic screening method for the detection of ochratoxin A in green coffee at a control level of 10 microg/kg.

A thin-layer chromatographic (TLC) screening method was developed for the detection of ochratoxin A (OTA) in green coffee at a control level of 10 microg/kg. The method is based on extraction of OTA with a mixture of phosphoric acid and dichloromethane, purification by liquid-liquid partition into sodium hydrogen carbonate, separation by normal-phase TLC, and detection by visual estimation of fluorescence intensity under a UV lamp at 366 nm. The method was validated by performing replicate analyses of uncontaminated green coffee material spiked at 3 different levels of OTA (5, 10, and 20 microg/kg), and also by comparing results obtained on a series of test trial green coffees naturally contaminated with OTA (range 0.2 to 136.7 microg/kg) with those measured by a quantitative immunoaffinity/HPLC method. The agreement between the two methods was excellent, and neither false positive nor false negative results were recorded. This screening method is rapid, simple, robust, and very cheap, which makes it particularly well adapted for implementation in coffee-producing countries.

Chromatography, Thin Layer↗
PubMed2002

Chemical profiling to differentiate geographic growing origins of coffee.

The objective of this research was to demonstrate the feasibility of this method to differentiate the geographical growing regions of coffee beans. Elemental analysis (K, Mg, Ca, Na, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, S, Cd, Pb, and P) of coffee bean samples was performed using ICPAES. There were 160 coffee samples analyzed from the three major coffee-growing regions: Indonesia, East Africa, and Central/South America. A computational evaluation of the data sets was carried out using statistical pattern recognition methods including principal component analysis, discriminant function analysis, and neural network modeling. This paper reports the development of a method combining elemental analysis and classification techniques that may be widely applied to the determination of the geographical origin of foods.

Africa, Eastern↗
PubMed2002

Characterization of free radicals in soluble coffee by electron paramagnetic resonance spectroscopy.

EPR spectra of soluble coffee display single-line free radical signals in both the solid state and aqueous solution, along with signals from the paramagnetic ions Fe(III) and Mn(II). The intensity of the free radical signal in the pure solid was estimated to be ca. 7.5 x 10(16) unpaired electrons/g, and there was no significant change on dissolution in water. In aqueous solutions, however, the free radical signal declined rapidly over ca. 10-15 min in the temperature range 20-65 degrees C, after which only slow changes were observed. This decline, which was essentially independent of atmosphere, was greatest for the lowest temperatures used, and the intensity after 1 h fitted well to an exponential curve with respect to temperature. The free radicals responsible for the single-peak EPR signal did not react with any of the spin traps tested in the present experiments, but unstable free radicals with parameters consistent with adducts of C-centered radicals were detected in coffee solutions in the presence of PBN and 4-POBN spin traps. The presence of oxygen in the solutions increased the initial rate of formation of these free radical adducts. No adducts were detected when DEPMPO was used as spin trap. However, *OH adducts of DEPMPO were shown to be unstable in the presence of coffee, a fact which illustrates the strong free radical scavenging ability of coffee solutions.

Coffee↗
PubMed2003

Investigation of the change in the flavor of a coffee drink during heat processing.

Heat processing is responsible for the change in the flavor of a coffee drink. In this study, the application of gas chromatography-olfactometry of headspace samples (GCO-H) using the vapor fraction before and after heat processing of the coffee samples resulted in the detection of 12 odor-active peaks for which the flavor dilution (FD) factors changed. Eight potent odorants were identified from these peaks by gas chromatography-mass spectrometry (GC-MS). Among these components, methanethiol (putrid), acetic acid (sour), 3-methylbutanoic acid (sour), 2-furfuryl methyl disulfide (meaty), and 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like) increased after heating of the coffee sample, whereas 2-furfurylthiol (roasty), methional (potato-like), and 3-mercapto-3-methylbutyl formate (roasty) decreased compared with the coffee sample before heat treatment. In addition, extensive studies have been carried out on the pH effects on the change in the concentration of 2-furfurylthiol during heat processing and in the pH range of 5-7; it was found that the concentration of this compound in the model solutions had significantly changed.

Beverages↗
PubMed2002

Chemical characterization and antioxidant properties of coffee melanoidins.

Melanoidins, the brown polymers formed through Maillard reaction during coffee roasting, constitute up to 25% of the coffee beverages' dry matter. In this study chemical characterization of melanoidins obtained from light-, medium-, and dark-roasted coffee beans, manufactured from the same starting material, was performed. Melanoidins were separated by gel filtration chromatography and studied by MALDI-TOF mass spectrometry. Results showed that the amount of melanoidins present in the brews increased as the intensity of the thermal treatment increased, while their molecular weight decreased. The antioxidant activity of melanoidins isolated from the different brews was studied by using different methodologies. Melanoidins antiradical activity determined by ABTS(*)(+) and DMPD(*)(+) assays decreased as the intensity of roasting increased, but the ability to prevent linoleic acid peroxidation was higher in the dark-roasted samples. Data suggest that melanoidins must be carefully considered when the relevance of coffee intake in human health is studied.

Antioxidants↗
PubMed2003

Antioxidant properties of ready-to-drink coffee brews.

The influence of some technological variables on the changes of the antioxidant capacity of ready-to-drink coffee brews was investigated. Results showed that, depending on the roasting degree as well as on the packaging conditions adopted, redox reactions, which can take place during storage, are responsible for significant changes in the overall antioxidant capacity of the product. In particular, the redox potential of air-packaged coffee brews, obtained from light- and medium-roasted beans, showed maximum values after 2 days of storage, which corresponded to a minimum in the chain-breaking activity, while, in the case of the dark-roasted sample packaged under ordinary atmosphere, both the redox potential and the chain-breaking activity showed a maximum around 2-3 days of storage. In contrast, in the absence of oxygen, the coffee brews maintained the initial reducing properties over all the storage time, although the radical-scavenging activity values changed in a way very similar to that of the air-packaged sample. These results suggested that the changes in the antioxidant properties of the coffee brews may be attributed to a further development of the Maillard reaction during storage.

Antioxidants↗
PubMed2004

Antioxidative activities of fractions obtained from brewed coffee.

The antioxidative activity of column chromatographic fractions obtained from brewed coffee was investigated to find antioxidants and to assess the benefit of coffee drinking. The dichloromethane extract inhibited hexanal oxidation by 100 and 50% for 15 days and 30 days, respectively, at the level of 5 microg/mL. A GC/MS analysis of fractions, which exhibited oxidative activity, revealed the presence of antioxidative heterocyclic compounds including furans, pyrroles, and maltol. The residual aqueous solution exhibited slight antioxidative activity. The inhibitory activity (%) of the seven fractions from an aqueous solution toward malonaldehde formation from lipid oxidation ranged from 10 to 90 at a level of 300 microg/mL. The results indicate that brewed coffee contains many antioxidants and consumption of antioxidant-rich brewed coffee may inhibit diseases caused by oxidative damages.

Aldehydes↗
PubMed2003

Effect of pH on the thermal stability of potent roasty odorants, 3-mercapto-3-methylbutyl esters, in coffee drink.

The effect of pH on the thermal stability of potent roasty odorants, 3-mercapto-3-methylbutyl esters, in coffee drinks was investigated. The concentration of 3-mercapto-3-methylbutyl formate in the coffee drink was drastically decreased during the heat processing. However, the residual ratio of this compound in the coffee drink adjusted to pH 5.0 was higher than that of pH 6.5. On the other hand, the residual ratios of 3-mercapto-3-methylbutyl acetate showed high values in the coffee drinks adjusted to both pHs. In the pH range of 3-7, the residual ratios of 3-mercapto-3-methylbutyl formate in aqueous model solutions varied depending on the pH value. It had a thermal stability maximum at pH 4.0, while 3-mercapto-3-methylbutyl acetate showed stability during heat processing over all the pH values tested. In addition, the residual ratios of the formate and acetate esters, which were composed of various alcohol derivatives, showed the same tendency as that of the 3-mercapto-3-methylbutyl esters. These results suggested that the low thermal stability and pH dependence of 3-mercapto-3-methylbutyl formate are based on the structure of the formate ester.

Acetates↗
PubMed2003

Analysis of ochratoxin a in coffee by solid-phase cleanup and narrow-bore liquid chromatography-fluorescence detector-mass spectrometry.

A method for the analysis of ochratoxin A (OTA) in green and roasted coffee has been developed. OTA was extracted from coffee with 1% NaHCO(3), and the extract was filtered and purified by solid-phase cleanup using a polymeric column that exhibits reversed-phase and anion-exchange functionalities. OTA was analyzed on a narrow-bore reversed-phase C(18) HPLC column with acetonitrile/water (0.1% formic acid) (40:60) as mobile phase and quantified with a fluorescence detector. The presence of OTA in coffee was confirmed by single-quadruple mass spectrometry using an electrospray ionization source. The method has been validated, obtaining a recovery of 82.5% and a detection limit of 0.1 ng/g. It has been applied to 20 coffee samples from various countries and different manufacturers with no detection of OTA.

Chromatography, High Pressure Liquid↗
PubMed2005

Interactions between volatile and nonvolatile coffee components. 2. Mechanistic study focused on volatile thiols.

This study is the second of two publications that investigate the interactions between volatile and nonvolatile components in coffee brew. The purpose here was to shed some light into the chemical mechanisms responsible for the decrease of volatile thiols when in contact with coffee nonvolatiles. A mixture of volatile thiols covering a large range of physicochemical properties was monitored over time in the presence of a coffee brew model. The binding potential was estimated by SPME-GC-MS. Additives inhibiting specific reaction pathways were preincubated with the coffee brew 1 h prior to addition of the volatile compounds. Degradation kinetics of the volatile thiols were characterized by their rate constants k(obs). The effect of individual additives was shown by calculating k(rel), the relative rate constant as compared to the reference without additive. The conclusion was that thiols, mainly responsible for the "roasty" and "burnt" notes, disappear via two main chemical mechanisms. The results suggest that nucleophilic addition is the major pathway for thiol degradation. Addition occurs on oxidized species generated in the matrix in the presence of air. This mechanism prevails for aliphatic thiols (e.g., ethanethiol, methanethiol). Benzylic thiols (such as 2-furfurylthiol) can react in parallel via another pathway that is slowed in the absence of oxygen and in the presence of a radical scavenger. This points to a radical mechanism, but further work is needed to support this hypothesis. A direct correlation between thiol hydrophobicity and the magnitude of the interactions was shown as well. Therefore, weak physical interactions or hydrophobic assistance accelerating chemical reactions cannot be excluded at this point of the study.

Chemical Phenomena↗
PubMed2005

Effect of roasting on properties of the zinc-chelating substance in coffee brews.

ApV is a brownish polymer with zinc-chelating activity in brewed coffee. We investigated in this study the effects of roasting on the zinc-chelating, reducing, and antioxidative activities of ApV from light-, medium-, and dark-roasted coffee. We also discuss the effect on the zinc-chelating activity of adding milk to the brewed coffee. The chelating activities of ApVs were evaluated by the tetramethyl murexide method. As the intensity of roasting increased, the yield of ApV increased, and the brown color and molecular weight of ApV respectively became darker and higher. Increasing the degree of roasting also decreased the zinc-chelating activity of ApV. The reducing activities of ApVs estimated by the indophenol method were stronger than those of ascorbic acid. Both the antioxidative activity estimated by the ABTS assay and the reducing activity of ApV increased with roasting. When milk was added to instant coffee and its ApV was prepared, the zinc-chelating activity of ApV was not changed.

Amino Acids↗
PubMed2006

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.

Acids, Carbocyclic↗
PubMed2006

Authentication of coffee by means of PCR-RFLP analysis and lab-on-a-chip capillary electrophoresis.

Coffee is one of the most important world food commodities, commercial trade consisting almost entirely of Arabica and Robusta varieties. The former is considered to be of superior quality and thus attracts a premium price. Methods to differentiate these coffee species could prove to be beneficial for the detection of either deliberate or accidental adulteration. This study describes a molecular genetics approach to differentiate Arabica and Robusta coffee beans. This employs a Polymerase Chain Reaction-Restriction Fragment Length Polymorphism to monitor a single nucleotide polymorphism within the chloroplastic genome. Samples were analyzed with a lab-on-a-chip capillary electrophoresis system. Coffee powder mixtures were analyzed with this technique, displaying a 5% limit of detection. The plastid copy number was found to be relatively constant across a wide range of bean samples, suggesting that this methodology can also be employed for the quantification of any adulteration of Arabica with Robusta beans.

Chloroplasts↗
PubMed2000

Screening on the occurrence of ochratoxin A in green coffee beans of different origins and types.

Since to our knowledge no data are available in the literature regarding the influence of green coffee type and origin on ochratoxin A (OTA) content, determinations were carried out in order to assess the level of OTA contamination in green coffee samples of different provenience. A total of 162 samples of green coffee beans from various countries (84 from Africa, 60 from America, and 18 from Asia) were analyzed for OTA. Both the amount and the variability of OTA levels were tested as a function of green coffee provenience. The results showed that 106 of the overall samples were positive for OTA, with concentration ranging from 0 to 48 microg/kg (ppb). In particular, it was possible to verify that African samples were more contaminated with respect to samples of other origin in terms of frequency and level of OTA; the highest concentrations observed were 18 and 48 microg/kg in two samples from The Congo.

Coffee↗
PubMed2000

Identification of proline-based diketopiperazines in roasted coffee.

Five proline-based diketopiperazines were identified in water extracts of roasted coffee proteins and roasted coffee itself. These are cyclo(pro-ile), cyclo(pro-leu), cyclo(pro-phe), cyclo(pro-pro), and cyclo(pro-val). The isolation included gel chromatography and solvent (CHCl(3)) extraction; in the case of roasted coffee brews, polyamide column chromatography was also used. The identification was achieved by LC-ESI-MS and -MS/MS by comparison of the retention time and the fragmentation pattern with reference compounds. As a second method GC-EI-MS was used. By both methods the presence of diketopiperazines in roasted coffee was unambiguously verified.

Coffee↗