Correlation of selected constituents with the total antioxidant capacity of coffee beverages: influence of the brewing procedure

Relationships between volatile and nonvolatile compounds and the antioxidant capacity of coffee brews prepared from commercial conventional and torrefacto roasted coffees, employing commonly used doses and prepared by four brewing procedures (filter, plunger, mocha, and espresso machine) were assessed. Significant correlations between volatile Maillard reaction products and antioxidant capacity (measured by both 2,2-diphenyl-1-picrylhydrazyl radical and redox potential methods) were not observed. Highly positive correlations between browned compounds and caffeine with both antioxidant capacity parameters were reported. Principal component analysis allowed coffee brews separation according to coffee roasting processes (PC1) and brewing procedures (PC2), showing that in all cases coffee brews from torrefacto roasted coffee were more antioxidant that those extracted from conventional ones; also, coffee brews extracted by an espresso machine were more antioxidant than those extracted by mocha, plunger, and filter machines.     

Changes in volatile compounds and overall aroma profile during storage of coffee brews at 4 and 25 degrees C

In this work, the chemical changes occurring in the volatile fraction of Arabica coffee brews during storage at 4 and 25 degrees C for 30 days have been characterized for the first time by means of HS-GC-MS. A total of 47 compounds were identified and quantified: 2 sulfur compounds, 7 aldehydes, 3 esters, 15 furans, 5 ketones, 1 alcohol, 2 thiophenes, 4 pyrroles, 1 pyridine, 5 pyrazines, 1 alkene, and 1 acid. No new volatile compounds were detected at the end of the storage time. The changes observed are, in general, slower and less pronounced at refrigeration temperature. Storage also affects the sensory characteristics of the stored coffee brews, which lose part of their aroma intensity and freshness, acquiring some nondesirable notes such as rancid aroma, mainly during storage at 25 degrees C. Furthermore, seven aroma indices have been proposed as indicators of coffee brew staling, which show a good correlation with some sensory attributes, not only for aroma but also overall sensory quality. Consequently, they could be considered useful to monitor both the "age" and the sensory quality of stored coffee brews.     

Chemical and sensorial characteristics of espresso coffee as affected by grinding and torrefacto roast

Grinding is a critical step in the preparation of espresso coffee (EC). The addition of sugar during the torrefacto roasting process could influence the degree of brittleness and grinding. The aim of this work was to study the influence of the grinding grades (coarse, fine, and very fine) in Arabica/Robusta 20:80, natural roasted (A20:R80), and Arabica/Robusta 20:80 with 50% Robusta torrefacto roasted (A20:R80 50% torrefacto) on the chemical and sensorial characteristics of EC in order to select the optimal espresso grinding grade. A higher percentage of coarse particles was found in A20:R80 ground coffee. In both ECs, the extraction of solids and soluble and aroma compounds increased inversely with particle size. Higher foam indices and extraction yields were found in A20:R80 50% torrefacto ECs probably due to the solubilization of caramelized sugar and melanoidins. It has been suggested that the range of an acceptable extraction yield could be extended to 25% in A20:R80 50% torrefacto ECs. In conclusion, the optimal grinding grade for the obtainment of an EC with A20:R80 was fine and that for A20:R80 50% torrefacto was coarse.     

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.     

Identification of odor-active 3-mercapto-3-methylbutyl acetate in volatile fraction of roasted coffee brew isolated by steam distillation under reduced pressure

In a roasted Arabica coffee brew, the potent roasty odor quality compound was identified as 3-mercapto-3-methylbutyl acetate by comparison of its Kovats gas chromatography retention index, mass spectrum, and odor quality to those of the synthetic authentic compound. 3-Mercapto-3-methylbutyl acetate has been identified for the first time in the coffee, and according to the results of the aroma extract dilution analysis, the contribution of this compound to the flavor of the roasted coffee brew varied depending on the degree of the coffee bean roasting. The concentration of this compound in the coffee brews as with 3-mercapto-3-methylbutyl formate increased with an increase in the degree of roasting. However, the slope of the amount of both esters was different, and 3-mercapto-3-methylbutyl acetate hardly increased with a low degree of roasting at more than a 21 luminosity (L)-value, but it rapidly increased when the roasting degree of the coffee beans reached the L-value of 18. These results suggested that the contribution of 3-mercapto-3-methylbutyl acetate to the overall flavor is peculiar to the flavor of the highly roasted coffee.     

Characterization of espresso coffee aroma by static headspace GC-MS and sensory flavor profile.

The aromas of three espresso coffee (EC) samples from different botanical varieties and types of roast (Arabica coffee, Robusta natural blend, and Robusta Torrefacto blend (special roast by adding sugar)) were studied by static headspace GC-MS and sensory flavor profile analysis. Seventy-seven compounds were identified in all of the EC samples. Among them, 13 key odorants have been quantified and correlated with their flavor notes by applying multivariate statistical methods. Some correlations have been found in the EC samples: some aldehydes with fruity flavors, diones with buttery flavors, and pyrazines with earthy/musty, roasty/burnt, and woody/papery flavors. By applying principal component analysis (PCA), Arabica and Robusta samples were separated successfully by principal component 1 (60.7% of variance), and Torrefacto and Natural Robusta EC samples were separated by principal component 2 (28.1% of total variance). With PCA, the aroma characterization of each EC sample could be observed. A very simple discriminant function using some key odorants was obtained by discriminant analysis, allowing the classification of each EC sample into its respective group with a success rate of 100%.     

Coffee dietary fiber contents and structural characteristics as influenced by coffee type and technological and brewing procedures

Coffee brews contain considerable amounts of soluble dietary fiber, mainly low substituted galactomannans and type II arabinogalactans. Factors possibly influencing the content and structures of dietary fiber in coffee brews, such as type of coffee, roasting and grinding degree, and brewing procedure, were studied. In addition, several commercial samples such as instant espresso, instant coffee, instant cappuccino, decaffeinated coffees, and coffee pads were analyzed. The dietary fiber contents of the coffee brews ranged from 0.14 to 0.65 g/100 mL (enzymatic-gravimetric methodology), proving an influence of the factors investigated. For example, the drip brew of an arabica coffee contained significantly more soluble dietary fiber than the drip brew of a comparable robusta coffee, and depending on the brewing procedure, the soluble dietary fiber content of beverages obtained from the same coffee sample ranged from 0.26 to 0.38 g/100 mL. Dietary fiber contents of coffee brews were enhanced only up to a certain degree of roast. Drip brews of decaffeinated arabica coffees (commercial samples) contained significantly less dietary fiber than any non-decaffeinated drip brew investigated in this study. The observed differences in the dietary fiber contents were accompanied by changes in the structural characteristics of fiber polysaccharides, such as galactomannan/arabinogalactan ratio, galactose substitution degree of mannans, or galactose/arabinose ratio of arabinogalactans as analyzed by methylation analysis.     

Analysis of volatile compounds released during the grinding of roasted coffee beans using solid-phase microextraction

A dynamic solid-phase microextraction (SPME) method to sample fresh headspace volatile compounds released during the grinding of roasted coffee beans was described and the analytical results using gas chromatography/mass spectrometry (GC/MS) and GC/olfactometry (GC/O) were compared to those of the conventional static SPME sampling methods using ground coffee. Volatile compounds released during the grinding of roasted coffee beans (150 g) were obtained by exposing the SPME fiber (poly(dimethylsiloxane)/divinylbenzene, PDMS/ DVB) for 8 min to nitrogen gas (600 mL/min) discharged from a glass vessel in which the electronic coffee grinder was enclosed. Identification and characterization of volatile compounds thus obtained were achieved by GC/MS and GC/O. Peak areas of 47 typical coffee volatile compounds, separated on total ion chromatogram (TIC), obtained by the dynamic SPME method, showed coefficients of variation less than 5% (n = 3) and the gas chromatographic profile of volatile compounds thus obtained was similar to that of the solvent extract of ground coffee, except for highly volatile compounds such as 4-hydroxy-2,5-dimethyl-3(2H)-furanone and 4-ethenyl-2-methoxyphenol. Also, SPME dilution analysis of volatile compounds released during the grinding of roasted coffee beans showed linear plots of peak area versus exposed fiber length (R (2) > 0.89). Compared with those of the headspace volatile compounds of ground coffee using GC/MS and GC/O, the volatile compounds generated during the grinding of roasted coffee beans were rich in nutty- and smoke-roast aromas.     

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.     

On the role of (-)-2-methylisoborneol for the aroma of Robusta coffee

The role of 2-methylisoborneol (MIB) in coffee aroma is controversially discussed in the literature. MIB is known as an off-flavor compound in drinking water and food, but it has also been suggested as a key flavor component of Robusta coffee, discriminating Robusta from Arabica coffee. To check this hypothesis the role of MIB in coffee brews was studied. Two reference samples containing pure Arabica and Robusta coffee brews were compared with five samples of Arabica coffee brews containing increasing amounts of MIB. The sensory panel consisting of 12 assessors perceived a distinct difference in the Arabica coffee odor and flavor in the presence of 10-25 ng/kg MIB, which is close to its threshold value in water. The sensory impression was described as musty, mold-like, and earthy. The intensity increased with increasing concentration of MIB. The panelists agreed that there was no similarity with the Robusta reference sample. The Arabica coffee brew spiked with MIB was no longer palatable due to the odor and flavor defect formed.     

Furan levels in coffee as influenced by species, roast degree, and brewing procedures

Brazilian green coffee beans of Coffea arabica and Coffea canephora species were roasted to light, medium, and dark roast degrees and analyzed in relation to furan content by using an in-house validated method based on gas chromatography coupled to mass spectrometry preceded by headspace solid-phase microextraction. Furan was not detected in green coffees, whereas levels between 911 and 5852 μg/kg were found in the roasted samples. Higher concentrations were found in Coffea canephora species and darker ground coffees. Some of the potential furan precursors were observed in significant amounts in green coffee, especially sucrose and linoleic acid, but their concentrations could not be correlated to furan formation. Additionally, coffee brews were prepared from roasted ground coffees by using two different procedures, and furan levels in the beverages varied from <10 to 288 μg/kg. The factor that most influenced the furan content in coffee brew was the brewing procedure.     

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.     

Influence of foam structure on the release kinetics of volatiles from espresso coffee prior to consumption

The relationship between the physical structure of espresso coffee foam, called crema, and the above-the-cup aroma release was studied. Espresso coffee samples were produced using the Nespresso extraction system. The samples were extracted with water with different levels of mineral content, which resulted in liquid phases with similar volatile profiles but foams with different structure properties. The structure parameters foam volume, foam drainage, and lamella film thickness at the foam surface were quantified using computer-assisted microscopic image analysis and a digital caliper. The above-the-cup volatile concentration was measured online by using PTR-MS and headspace sampling. A correlation study was done between crema structure parameters and above-the-cup volatile concentration. In the first 2.5 min after the start of the coffee extraction, the presence of foam induced an increase of concentration of selected volatile markers, independently if the crema was of high or low stability. At times longer than 2.5 min, the aroma marker concentration depends on both the stability of the crema and the volatility of the specific aroma compounds. Mechanisms of above-the-cup volatile release involved gas bubble stability, evaporation, and diffusion. It was concluded that after the initial aroma burst (during the first 2-3 min after the beginning of extraction), for the present sample space a crema of high stability provides a stronger aroma barrier over several minutes.     

采用气相色谱-离子迁移谱分析黄大茶加工过程挥发性成分

茶叶加工对茶叶香气的形成至关重要。为了研究黄大茶加工过程中香气成分的组成及变化规律,采用气相色谱-离子迁移谱(Gas Chromatography-Ion Mobility Spectrometry,GC-IMS)技术对黄大茶加工过程的挥发性成分进行分析。定性分析、鉴定茶叶挥发性成分,构建黄大茶加工过程挥发性成分的差异谱图,并以鉴定的挥发性成分对黄大茶加工过程进行主成分分析。共鉴定出挥发性成分40种,主要有醇类、酮类、醛类、酯类和杂环类化合物。杂环类和醛类化合物是黄大茶挥发性成分的主体部分,且杀青之后,杂环类化合物的含量随着加工过程的进行逐渐增加,醛类化合物的相对含量在初烘之后呈现显著性增加,而醇类及酮类挥发性成分的相对含量在初烘之后显著性降低(P0.05)。具花香的氧化芳樟醇只在初闷之前的样品中得到鉴定,在鲜叶中的含量最高,达21.98%,而1-辛烯-3-酮及苯乙酮只在初烘之后的样品中得到鉴定。通过GC-IMS的指纹图谱可知,苯甲醛、2,5-二甲基呋喃、糠醛及二甲基二硫等挥发性成分构成了经"拉老火"工序的黄大茶的特征峰区域。在一定程度上,主成分分析能够将黄大茶加工过程样品进行区分,表明气相色谱-离子迁移谱分析可为黄大茶加工过程的判别区分提供可能。相较于传统的茶叶挥发性成分检测分析技术,气相色谱-离子迁移谱具有快速、高效、绿色环保的特点。研究结果提供一种新的茶叶挥发性成分的检测分析方法,同时为茶叶加工过程监测及品质控制等提供了一定参考依据和理论基础。     

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.     

Factors influencing the norharman and harman contents in espresso coffee

Espresso coffee (EC) brews were analyzed for beta-carboline [norharman (NH) and harman (H)] contents, by RP-HPLC with fluorescence detection. The influence of the coffee species (arabica or robusta), the roast degree, and the brew length was studied. The results show that the content of NH and H in EC is dependent primarily on the coffee species, followed by brew length. The roast degree has only a minor influence on the final content of NH and H in EC. When compared with other coffee brews, EC has an amount of these beta-carbolines (in micrograms per liter) similar to that of mocha coffee, both being more concentrated than filter and press-pot coffees. Therefore, the consumer's preferences will determine the amount of NH and H ingested daily. For the caffeinated 30 mL of EC, the arabica coffees contain about 4.08 microg of NH and 1.54 microg of H. Commercial blends (usually with a maximum of 30% robusta) range from the cited arabica values to 10.37 microg of NH and 4.35 microg of H.     

Volatiles from roasted byproducts of the poultry-processing industry

Volatiles of roasted chicken breast muscle and byproducts, such as backbones, breastbones, spent bones, and skin, were investigated. Total volatile concentrations ranged from 2030 ppb in the roasted backbones to 4049 ppb in the roasted skin. The major classes of volatile compounds detected in roasted samples were aldehydes (648-1532 ppb) and alcohols (336-1006 ppb). Nitrogen- and/or sulfur-containing compounds were also detected in appreciable quantities (161-706 ppb) in all samples. For all samples, hexanal and 2-methyl-2-buten-1-ol were dominant among the aldehydes and alcohols, respectively. Among the nitrogen- and sulfur-containing compounds, Maillard reaction products, such as tetrahydropyridazines, piperidines, and thiazoles, were the major contributors to the total volatile content in all samples. The composition of volatiles observed in roasted byproducts was markedly different from that of the roasted breast muscle. Therefore, the blending of the byproducts in appropriate proportions or blending of volatile flavor extracts from different byproducts may be necessary to obtain an aroma that mimics roasted chicken aroma.     

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.     

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.