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.     

Determination of acrylamide during roasting of coffee

In this study different Arabica and Robusta coffee beans from different regions of the world were analyzed for acrylamide after roasting in a laboratory roaster. Due to the complex matrix and the comparably low selectivity of the LC-MS at m/ z 72, acrylamide was analyzed after derivatization with 2-mercaptobenzoic acid at m/ z 226. Additionally, the potential precursors of acrylamide (3-aminopropionamide, carbohydrates, and amino acids) were studied. The highest amounts of acrylamide formed in coffee were found during the first minutes of the roasting process [3800 ng/g in Robusta ( Coffea canephora robusta) and 500 ng/g in Arabica ( Coffea arabica)]. When the roasting time was increased, the concentration of acrylamide decreased. It was shown that especially the roasting time and temperature, species of coffee, and amount of precursors in raw material had an influence on acrylamide formation. Robusta coffee contained significantly larger amounts of acrylamide (mean = 708 ng/g) than Arabica coffee (mean = 374 ng/g). Asparagine is the limiting factor for acrylamide formation in coffee. 3-Aminopropionamide formation was observed in a dry model system with mixtures of asparagine with sugars (sucrose, glucose). Thermal decarboxylation and elimination of the alpha-amino group of asparagine at high temperatures (>220 degrees C) led to a measurable but low formation of acrylamide.     

Potent odorants of raw Arabica coffee. Their changes during roasting

Aroma extract dilution analysis of raw Arabica coffee revealed 3-isobutyl-2-methoxypyrazine (I), 2-methoxy-3,5-dimethylpyrazine (II), ethyl 2-methylbutyrate (III), ethyl 3-methylbutyrate (IV), and 3-isopropyl-2-methoxypyrazine (V) as potent odorants. The highest odor activity value was found for I followed by II, IV, and V. It was concluded that I was responsible for the characteristic, peasy odor note of raw coffee. Twelve odorants occurring in raw coffee and (E)-beta-damascenone were also quantified after roasting. The concentration of I did not change, whereas methional, 3-hydroxy-4, 5-dimethyl-2(5H)-furanone, vanillin, (E)-beta-damascenone, and 4-vinyl- and 4-ethylguaiacol increased strongly during the roasting process.     

Identification and in vitro cytotoxicity of ochratoxin A degradation products formed during coffee roasting

The mycotoxin ochratoxin A is degraded by up to 90% during coffee roasting. In order to investigate this degradation, model heating experiments with ochratoxin A were carried out, and the reaction products were analyzed by HPLC-DAD and HPLC-MS/MS. Two ochratoxin A degradation products were identified, and their structure and absolute configuration were determined. As degradation reactions, the isomerization to 14-(R)-ochratoxin A and the decarboxylation to 14-decarboxy-ochratoxin A were identified. Subsequently, an analytical method for the determination of these compounds in roasted coffee was developed. Quantification was carried out by HPLC-MS/MS and the use of stable isotope dilution analysis. By using this method for the analysis of 15 coffee samples from the German market, it could be shown that, during coffee roasting, the ochratoxin A diastereomer 14-(R)-ochratoxin A was formed in amounts of up to 25.6% relative to ochratoxin A. The decarboxylation product was formed only in traces. For toxicity evaluations, first preliminary cell culture assays were performed with the two new substances. Both degradation products exhibited higher IC50 values and caused apoptotic effects with higher concentrations than ochratoxin A in cultured human kidney epithelial cells. Thus, these cell culture data suggest that the degradation products are less cytotoxic than ochratoxin A.     

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.     

Incidence,level, and behavior of aflatoxins during coffee bean roasting and decaffeination

Screening for aflatoxins (Afs), isolation and identification of Aspergillus flavus, and the effect of decaffeination and roasting on the level of contamination in coffee beans are studied. The percent frequency of A. flavus ranged between 4 and 80% in green coffee beans (GCB), whereas in ground roasted coffee beans (GRCB), it ranged between 1 and 71%. Aflatoxins were detected in 76.5 and 54.6% of the infected samples with averages of 4.28 and 2.85 microg/kg of GCB and GRCB, respectively. Roasting was demonstrated to lower the concentration of Afs in GCB. The Afs levels were reduced by approximately 42.2-55.9% depending on the type and temperature of roasting. The highest yields of Afs were detected in the decaffeinated green coffee beans (24.29 microg/kg) and roasted coffee beans (16.00 microg/kg). The growth of A. flavus in liquid medium containing 1 or 2% caffeine was reduced by 50%, and the level of aflatoxin in the medium was undetectable.     

Influence of roasting levels on ochratoxin a content in coffee

Because of inconsistent and contradictory results from investigations concerning the influence of roasting process on the ochratoxin A content in coffee beans, a study was undertaken to assess the elimination of ochratoxin A during the roasting process. Four different green coffee samples, naturally contaminated with ochratoxin A, were submitted to different roasting conditions (light, medium, and dark) and analyzed for roasting parameters (weight loss, color change, density, and moisture content) and ochratoxin A content. The ochratoxin A content of green coffee was reduced by the roasting process; in particular, consistently high percentages of ochratoxin A reduction were found in the highest contaminated samples. This reduction was influenced by the severity of the thermal process and was generally related to the initial ochratoxin A content. Samples obtained with roasting parameters suitable for a typical Italian espresso coffee brew showed reductions of >90% in the ochratoxin A content, in both high and low contaminated samples. Moreover, the presence of off-flavors and visual defects was not found to be directly related to the ochratoxin A content in the green coffee samples.     

Changes in key aroma compounds of Criollo cocoa beans during roasting

Application of a comparative aroma extraction dilution analysis on unroasted and roasted Criollo cocoa beans revealed 42 aroma compounds in the flavor dilution (FD) factor range of 1-4096 for the unroasted and 4-8192 for the roasted cocoa beans. While the same compounds were present in the unroasted and roasted cocoa beans, respectively, these clearly differed in their intensity. For example, 2- and 3-methylbutanoic acid (rancid) and acetic acid (sour) showed the highest FD factors in the unroasted beans, while 3-methylbutanal (malty), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), and 2- and 3-methylbutanoic acid (sweaty) were detected with the highest FD factors in the roasted seeds. Quantitation of 30 odorants by means of stable isotope dilution assays followed by a calculation of odor activity values (ratio of the concentration/odor threshold) revealed concentrations above the odor threshold for 22 compounds in the unroasted and 27 compounds in the roasted cocoa beans, respectively. In particular, a strong increase in the concentrations of the Strecker aldehydes 3-methylbutanal and phenylacetaldehyde as well as 4-hydroxy-2,5-dimethyl-3(2H)-furanone was measured, suggesting that these odorants should contribute most to the changes in the overall aroma after roasting. Various compounds contributing to the aroma of roasted cocoa beans, such as 3-methylbutanoic acid, ethyl 2-methylbutanoate, and 2-phenylethanol, were already present in unroasted, fermented cocoa beans and were not increased during roasting.     

Modeling the formation of some polycyclic aromatic hydrocarbons during the roasting of Arabica coffee samples

Roasting is a critical process in coffee production, as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot-spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, for roasting conditions ranging from 5 to 20 min. Several PAHs were determined in both roasted coffee samples and green coffee samples. Different models were tested, with more or less assumptions on the chemical phenomena, with a view to predict the system global behavior. Two kinds of models were used and compared: kinetic models (based on Arrhenius law) and statistical models (neural networks). The numbers of parameters to adjust differed for the tested models, varying from three to nine for the kinetic models and from five to 13 for the neural networks. Interesting results are presented, with satisfactory correlations between experimental and predicted concentrations for some PAHs, such as pyrene, benz[a]anthracene, chrysene, and anthracene.     

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.     

FTIR-ATR analysis of brewed coffee: effect of roasting conditions

FTIR-ATR was used to study the effect of roasting conditions on the flavor of brewed coffee using Guatemala Antigua coffee beans. The 1800-1680 cm(-1) carbonyl region for vinyl esters/lactones, esters, aldehydes, ketones, and acids was found to provide a flavor-print of the brewed coffee. A study of light, medium, and dark roasts indicated that when the rate of heating to the onset of the first and second cracks was kept constant, the types of carbonyl compounds formed were similar, varying only in their concentration. This difference in concentration is apparently due to the additional heating of the coffee bean beyond the second crack. When the heating rate to the onset of the first and second crack was varied, both the types and concentration of the carbonyl compounds formed during roasting were affected. Thus, heating rates of green coffee beans to the onset of the first and second cracks are important determinants of the basic taste and aroma of brewed coffee.     

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.     

Effect of roasting conditions on the polycyclic aromatic hydrocarbon content in ground Arabica coffee and coffee brew

Roasting is a critical process in coffee production as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, using both dark (20 min) and light (5 min) roasting conditions. Several PAHs were determined in both roasted coffee samples and green coffee samples. Also, coffee brews, obtained using an electric coffee maker, were analyzed for final estimation of PAH transfer coefficients to the infusion. Formation of phenanthrene, anthracene, and benzo[a]anthracene in coffee beans was observed at temperatures above 220 degrees C, whereas formation of pyrene and chrysene required 260 degrees C. Low levels of benzo[g,h,i]perylene were also noted for dark roasting under 260 degrees C, with simultaneous partial degradation of three-cycle PAHs, suggesting that transformation of low molecular PAHs to high molecular PAHs occurs as the roasting degree is increased. The PAH transfer to the infusion was quite moderate (<35%), with a slightly lower extractability for dark-roasted coffee as compared to light-roasted coffee.     

Effect of roasting on the formation of chlorogenic acid lactones in coffee

Of all plant constituents, coffee has one of the highest concentrations of chlorogenic acids. When roasting coffee, some of these are transformed into chlorogenic acid lactones (CGL). We have studied the formation of CGL during the roasting of coffee beans in Coffea arabica cv. Bourbon; C. arabicacv. Longberry; and C. canephora cv. Robusta. Individual CGL levels were determined by comparison of HPLC peaks with those of synthetic CGL standards. Seven CGL were identified: 3-caffeoylquinic-1,5-lactone (3-CQL), 4- caffeoylquinic-1,5-lactone (4-CQL), 3-coumaroylquinic-1,5-lactone (3-pCoQL), 4-coumaroylquinic-1,5-lactone (4-pCoQL), 3-feruloylquinic-1,5-lactone (3-FQL), 4-feruloylquinic-1,5-lactone (4-FQL), and 3,4-dicaffeoylquinic-1,5-lactone (3,4-diCQL). 3-CQL was the most abundant lactone in C. arabica and C. canephora, reaching peak values of 230 +/- 9 and 254 +/- 4 mg/100 g (dry weight), respectively, at light medium roast ( approximately 14% weight loss). 4-CQL was the second most abundant lactone (116 +/- 3 and 139 +/- 2 mg/100 g, respectively. The maximum amount of CGL represents approximately 30% of the available precursors. The relative levels of 3-CQL and 4-CQL in roasted coffee were reverse to those of their precursors in green coffee. This suggests that roasting causes isomerization of chlorogenic acids prior to the formation of lactones and that the levels of lactones in roasted coffee do not reflect the levels of precursors in green coffee.     

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.     

Changes in the concentrations of acrylamide, selected odorants, and catechins caused by roasting of green tea

This research aims to optimize roasted green tea (Houjicha) processing by using roasting treatments to achieve acrylamide mitigation without compromising the quality. 2-Ethyl-3,5-dimethylpyrazine and 2-ethyl-3,6-dimethylpyrazine were identified as potent odorants by aroma extract dilution analysis. In preliminary sensory experiments, the desirable Houjicha flavor was produced in products roasted at 160 degrees C for 30 min and at 180 degrees C for 15 min. Under these conditions, potent odorants were formed at levels adequate for contributing to the Houjicha flavor. Acrylamide amounts in tea infusions were 2.0 and 4.0 microg/L by roasting at 160 degrees C for 30 min and at 180 degrees C for 15 min, respectively. Compared to roasting at 180 degrees C, the degradation of tea catechins was suppressed by roasting at 160 degrees C. Hence, roasting at 160 degrees C for is recommended for Houjicha processing for acrylamide mitigation, formation of potent odorants, and suppression of degradation of tea catechins.     

Changes in key odorants of raw coffee beans during storage under defined conditions

During storage of raw coffee beans (green coffee) atypical odors may develop, which are suggested to influence the aroma of particularly the coffee beverage. To gain insight into the aroma compounds responsible for such odor changes, a comparative aroma extract dilution analysis was applied on unstored, raw Arabica coffee beans from Colombia (water content=11.75%) and on the same beans with a water content of 13.5%, which were stored for 9 months at 40 degrees C. In combination with the flavor dilution (FD) factors, the results of the identification experiments showed strong increases in (E)-beta-damascenone (cooked apple-like), 2-methoxy-4-vinylphenol (clove-like), and methyl 2-methyl- and methyl 3-methylbutanoate (fruity), whereas others, such as the earthy smelling 3-isopropyl-2-methoxypyrazine as well as 2-phenylethanol and 3-methoxyphenol, remained unchanged during storage. In addition, the previously unknown coffee odorant 2-methoxy-5-vinylphenol (intense smoky odor) increased significantly during storage. Quantitative measurements performed on raw coffee samples stored at various temperatures, water contents, and oxygen availabilities indicated that the significant increase of, in particular, the methyl esters of 2- and 3-methylbutanoic acid were responsible for the pronounced and fruity odor quality perceived in the stored green coffee, whereas the higher concentrations of 2-methoxy-4-vinylphenol and 2-methoxy-5-vinylphenol led to the more pronounced smoky, clove-like odor quality. On the basis of the results obtained, in particular the reduction of the water content in combination with lower temperatures can be suggested to avoid aroma changes in raw coffee beans caused by storage.     

基于电子鼻技术检测不同焙烤程度咖啡的特征性香气

为研究咖啡香气与焙烤条件的联系,进一步提供合理的加工条件生产特定香气的咖啡,减少咖啡多样化的生产成本。以海南阿拉比卡咖啡豆为试材,利用固相微萃取的气质联用(solid phase microextraction-gas chromatographic-mass spectrometric,SPME-GC-MS)结合电子鼻对不同焙烤温度处理6 min的咖啡挥发性化合物和特征性香气进行检测。结果表明:咖啡中总共检测出43种化合物,咖啡在30(室温)、80、100℃时挥发性组分主要为醇类、醚类与胺类以致香气不足,随着温度继续升高,逐渐热解生成芳香化合物,咖啡在120℃时开始出现糠醛、吡嗪与吡咯等,呋喃、醛类、吡嗪和吡咯的含量均在140℃时达到峰值,吡唑和咪唑只在160℃时产生且质量分数为2%~3%;电子鼻传感器T30/1、70/2、PA/2、P30/2与LY2/AA能有效地分析咖啡香气变化,主成分分析(principal component analysis,PCA)与判别因子分析(discriminant factorial analysis,DFA)有效地区分了不同焙烤程度的咖啡香气,层序聚类分析(hierarchical cluster analysis,HCA)成功将咖啡分为未焙烤、浅度焙烤、中度焙烤和深度焙烤四类。结果表明,随着焙烤温度的上升,咖啡中芳香醛、酚类、呋喃、吡嗪、吡咯和咪唑等挥发性化合物不断增加,进而改变咖啡的特征性香气,SPME-GC-MS结合电子鼻技术能实现咖啡挥发性组分、香气表型和焙烤程度三者之间有机地结合,以用于对咖啡焙烤程度的区别,该研究结果为生产某些特定香气咖啡的工艺提供科学依据和技术支持。     

Changes in antioxidant and metabolite profiles during production of tomato paste

Tomato products and especially concentrated tomato paste are important sources of antioxidants in the Mediterranean diet. Tomato fruit contain well-known antioxidants such as vitamin C, carotenoids, flavonoids, and hydroxycinnamic acids. The industrial processing of this fruit into tomato paste involves several treatments that potentially affect the final profile of antioxidants and other metabolites in the commercial product. Here we have used both biochemical and metabolomic techniques to assess the effect of each separate step in the industrial production chain starting from fresh fruit to the final tomato paste. Material was collected from five independent tomato paste production events spread over two successive years. Samples comprised the intact ripe fruits and semifinished products after fruit-breaking, separation of the pulp from skin and seeds, evaporation, and finally after canning and pasteurization. The effect of each processing step was determined by different types of analysis. First, the total antioxidant capacity and total phenolic content were determined by commonly used spectrophotometric methods. Second, individual antioxidants in the extracts were identified and compared using an HPLC with online antioxidant detection. Third, in each sample the levels of the major individual antioxidants present, i.e., vitamin C, phenolic compounds (such as rutin and chlorogenic acid), tocopherols, and carotenoids, were quantified. Fourth, an untargeted metabolomic approach using LC-QTOF-MS was used to identify those production steps that have the largest impact on the overall metabolic profile in the final paste as compared to the original fruits. This multifaceted approach has revealed that each processing step induces specific alterations in the metabolic profile, as determined by the different analysis procedures, and that in particular the fruit-breaking step and the removal of seed and skin significantly affect the levels of antioxidants and many other metabolites present in commercial tomato paste.     

Real-time monitoring of 4-vinylguaiacol,guaiacol, and phenol during coffee roasting by resonant laser ionization time-of-flight mass spectrometry

The formation of 4-vinylguaiacol, guaiacol, and phenol during coffee roasting was monitored in real-time, using resonance enhanced multiphoton ionization and time-of-flight mass spectrometry. A model is proposed, based on two connected reaction channels. One channel, termed the "low activation energy" channel, consists of ester hydrolysis of 5-FQA followed by decarboxylation of the ferulic acid to form 4-vinylguaiacol, and finally polymerization at the vinyl group to form partly insoluble polymers (coffee melanoidins). The second "high activation energy" channel opens up once the beans have reached higher temperatures. It leads to formation of guaiacol, via oxidation of 4-vinylguaiacol, and subsequently to phenol and other phenolic VOCs. This work aims at developing strategies to modify the composition of coffee flavor compounds based on the time-temperature history during roasting.