Factors affecting tocopherol contents in coffee brews: NP-HPLC/FLD,RP-UPLC-ESI/MSn and spectroscopic study

Qualitative and quantitative determination of tocopherols in filtered and unfiltered coffee brews was investigated. The NP-HPLC/FLD and RP-UPLC-ESI/MSⁿ techniques as well as fluorescence spectroscopy turned out to be very useful tools not only to estimate tocopherol contents, but also to detect contaminants in coffee brew tocopherol extracts. In all analysed coffee brew samples, only α- and β-T were detected. In Arabica coffee brews, the content of the β homologue was three to four times higher than that of the α homologue; however, in Robusta, they were almost identical. Unfiltered coffee brews contained about ten times more tocopherols, 3.02–5.26 and 3.39–16.52, than filtered brews, 0.4–0.71 and 1.26–1.77 μg/100 ml for α-T and β-T, respectively. The reduction in the size of ground coffee beans from 0.7 to 0.3 mm increases the concentration of tocopherols almost three times. Suspended coffee bean dust was the main source of tocopherols in coffee brews.     

Usage of Capillary Isotachophoresis and Antioxidant Capacity Measurement in Analysis of Changes in Coffee Properties After Roasting,Steaming and Decaffeination

The aim of the study was to optimise and validate the method for quantitation of short-chained organic acids in coffee brews by capillary isotachophoresis (ITP). The linearity of the method was satisfactory with R ² from 0.9924 for lactic acid to 0.9998 for acetic acid. The limit of detection (LOD) was from 4.9 μmol L^?1 for acetic acid to 24.8 μmol L^?1 for lactic acid. Precision of the method was from 0.20 to 2.69 %. This method was successfully applied to determine six organic acids (tartaric, formic, citric, malic, lactic and quinic) in Arabica and Robusta green and roasted coffee brews. The roasting as well as steaming and decaffeination processes of beans influenced degradation of acids (citric and malic) and their formation (quinic, tartaric, lactic and formic) in coffee brews. The influence of coffee processing on the antioxidant capacity of coffee brews was also tested by using the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), Folin-Ciocalteu and chelating Fe(II) assays. The roasted coffee brews possessed higher antioxidant capacity than unprocessed coffee brews, excluding chelating activity.     

Peroxyl radical-scavenging activity of coffee brews

The ORAC_FL assay was used in non-automated mode to evaluate the specific peroxyl radical scavenging properties of the aqueous soluble components of green and roasted Arabica and Robusta coffee samples. A relationship between ORAC_FL and the concentration of CQAs (caffeoyl quinic acids) was found for the extracts from green coffee beans. Aqueous extracts from roasted coffee beans possessed equal or stronger scavenging power than that obtained for the green coffee beans extracts and the scavenging activity depended on the variety of coffee and the roasting conditions. Brews from Robusta coffee beans showed the highest ORAC_FL. The best scavenging properties for the brews from Arabica coffee beans were detected in samples prepared from coffee beans roasted under light conditions. The data indicate that, during roasting, a complex network of reactions takes place leading to the formation of a wide number of compounds possessing specific scavenging properties. Under mild roasting conditions, caffeoyl quinic acids appear to be the main components responsible for the free radical scavenging power of coffee brews. In contrast, Maillard reaction products may be the principal components with free radical scavenging activity in more severely (medium and dark) roasted coffees.     

DITERPENES AND DITERPENE ESTERS IN COFFEE

Coffee oil contains pentacyclic diterpenes as typical lipid constituents which have not been detected in any other foods. Major representatives are 16-O-methylcafestol, cafestol, and kahweol. Cafestol is contained in Arabica as well as in Robusta coffee. 16-O-Methylcafestol is found only in Robusta coffee. Larger quantities of kahweol were detected in Arabica coffee, but only trace amounts are present in Robusta.

In coffee oil, the diterpenes are hardly present in free form. They are largely esterified with fatty acids. Up to 14 fatty acid esters of 16-O-methylcafestol and cafestol have been identified. Palmitate followed by linoleate, oleate, stearate, arachidate, and behenate comprise almost 98% of the acid moieties. In Robusta coffee, the total amount of these six 16-O-methylcafestol esters are between 1.0 and 3.0 g/kg d.m. The contents of the corresponding cafestol esters vary between 2.0 and 8.0 g/kg d.m. in Robusta coffee and 9.0 and 22.0 g/kg d.m. in Arabica coffee.

Roasting has little influence on the percentage compositions of the diterpene ester fractions. Accordingly, the percentage distribution of diterpene esters in coffee powder is reflected in the resulting coffee brew. The absolute amounts depend on the type of preparation. In Scandinavian-type coffee, about 23% of the diterpene esters present in the powder can be found in the beverage. The lowest amount (0.3% of the initial quantity) is found in filtered coffee. An intermediate position is taken by espresso coffee with up to 2.5% of the initial concentration.     

Coffee beans microstructural changes induced by cultivation processing: An X-ray microtomographic investigation

The present work reports on the microstructural characterisation of four types of different processed coffee beans, Coffea arabica, Arabica monsooned, Coffea canephora and Robusta monsooned, by means of X-ray microtomography technique (μCT). A three dimensional (3-D) quantitative analysis was carried out on the microstructure the bean samples before and after roasting. The 3-D microstructure information provides a better understanding of the structure of the beans and from an engineering perspective; knowledge about the microstructure can be used to identify the important processing parameters that affect the quality of coffee. With regards to the microstructure, the porosity increase can summarise the overall effects of the roasting process on coffee beans. Results demonstrate the success of μCT for the quantification of the microstructural alterations of the coffee beans induced by their different cultivation processes before and after the roasting process.     

DITERPENES AND DITERPENE ESTERS IN COFFEE

Coffee oil contains pentacyclic diterpenes as typical lipid constituents which have not been detected in any other foods. Major representatives are 16-O-methylcafestol, cafestol, and kahweol. Cafestol is contained in Arabica as well as in Robusta coffee. 16-O-Methylcafestol is found only in Robusta coffee. Larger quantities of kahweol were detected in Arabica coffee, but only trace amounts are present in Robusta.

In coffee oil, the diterpenes are hardly present in free form. They are largely esterified with fatty acids. Up to 14 fatty acid esters of 16-O-methylcafestol and cafestol have been identified. Palmitate followed by linoleate, oleate, stearate, arachidate, and behenate comprise almost 98% of the acid moieties. In Robusta coffee, the total amount of these six 16-O-methylcafestol esters are between 1.0 and 3.0 g/kg d.m. The contents of the corresponding cafestol esters vary between 2.0 and 8.0 g/kg d.m. in Robusta coffee and 9.0 and 22.0 g/kg d.m. in Arabica coffee.

Roasting has little influence on the percentage compositions of the diterpene ester fractions. Accordingly, the percentage distribution of diterpene esters in coffee powder is reflected in the resulting coffee brew. The absolute amounts depend on the type of preparation. In Scandinavian-type coffee, about 23% of the diterpene esters present in the powder can be found in the beverage. The lowest amount (0.3% of the initial quantity) is found in filtered coffee. An intermediate position is taken by espresso coffee with up to 2.5% of the initial concentration.     

Effect of different extraction methods on the recovery of chlorogenic acids,caffeine and Maillard reaction products in coffee beans

Water and ethanolic extracts were obtained from green and roasted (3 different roast degrees) Arabica and Robusta coffee beans. Three types of water extracts were prepared from the examined, finely ground material through: (a) brewing with boiling water, (b) boiling in water, and (c) boiling in water under elevated pressure. All these extracts were lyophilized. Two types of ethanolic extracts were derived from the examined material through (a) extraction of the finely ground coffee beans and (b) extraction of the solid residue that remained after boiling the coffee beans in water under elevated pressure. These ethanolic extracts were dried. Both water and ethanolic extracts were analyzed for concentration of potential antioxidants such as chlorogenic acids and caffeine (by HPLC) and Maillard reaction products (measurements of absorbance at 420 nm). Concentration of chlorogenic acids in Robusta extracts varied between 0.4 and 36.0 g × 100 g⁻¹ dry extract weight (db.), while in Arabica extracts it ranged from 0.1 to 22.4 g × 100 g⁻¹ db. Extracts of dark roasted Arabica contained more chlorogenic acids than those of Robusta. Concentration of caffeine, which in green and roasted coffee beans is maintained at the similar level, tended to increase in Robusta extracts with the roast degree and temperature of extraction with water, while in case of Arabica extracts there was no noticeable tendency. Caffeine concentrations varied between 0.12 and 8.41 g × 100 g⁻¹ db. and between 0.03 and 6.53 g × 100 g⁻¹ db. in Robusta and Arabica extracts, respectively. Ethanolic extracts were characterized by relatively higher caffeine concentrations and lower contents of brown pigments and chlorogenic acids as compared to water extracts. The richest in antioxidants were extracts of green Robusta coffee beans derived through boiling in water under elevated pressure.     

Use of methylpyrazine ratios to monitor the coffee roasting

The formation of methylpyrazines has been determined in roasted coffee beans (Arabica and Robusta). The determination of different methylpyrazines was studied by the coupled steam distillation-microdistillator as extraction method and gas chromatography using a capillary column and a thermionic detector.

The pyrazine; 2-methyl-; 2,3-dimethyl-; 2,5-dimethyl-; 2,6-dimethyl-; trimethyl- and tetramethyl pyrazine were detected in coffee beans. The principal compound was 2-methylpyrazine. The concentration of the latter pyrazine was more than 2000 μg/100 g of coffee beans depending on the time, the temperature of roasting and the origin of the beans. The correlation of the methylpyrazine quantity with the sensory analysis of the beans has shown the possibility of monitoring the roasting process of coffee beans.     

Influence of roasting and brew preparation on the ochratoxin A content in coffee infusion

A study of the effect of coffee processing in the ochratoxin A (OTA) level has been carried out from the green beans to the drinking form. The analysis of OTA has been carried out by an in-house validated HPLC method with fluorescence detection. The limits of detection were 0.04 µg/kg for green and roasted coffee, and 0.01 µg/L for coffee brew. Thirty-six green coffee samples of different origin (Colombia, Costa Rica, Brazil, Vietnam, India and Uganda) were analysed. The highest concentrations of OTA were found in Vietnamese samples - Robusta species treated by dry processing - (range 0.64-8.05 µg/kg), that also showed the highest percentage of defective beans (7.6%). These contaminated samples were roasted in a process that controlled loss of weight and color, as in the industry. A mean reduction of 66.5% was obtained, but the reduction seems to be heterogeneous. Coffee brew was prepared by the three brewing processes more utilized in Europe: moka, auto-drip and espresso. A reduction of the OTA level has been attained, being greater when using a espresso coffee maker (49.8%) than when using auto-drip (14.5%) or moka brewing (32.1%). Therefore, the method of coffee brew preparation plays a key role in the final OTA human exposure.     

Screening and distinction of coffee brews based on headspace solid phase microextraction/gas chromatography/principal component analysis

The volatile profiles of espresso and plunger (cafetière) coffees prepared from (1) an 80:20 (w/w) blend of natural roasted Robusta and Arabica (Robusta Natural blend), (2) a 40:40:20 (w/w/w) blend of Robusta Natural blend, Robusta torrefacto roast (850 g kg^?1 Robusta, 150 g kg^?1 sugar) and (3) natural roasted pure Arabica were established by headspace solid phase microextraction (SPME) after selection of the fibre coating (polyacrylate or polydimethylsiloxane) and the temperature and time of extraction. For the analysis of furans and indoles the polyacrylate coating proved to be more suitable; however, for the overall characterisation of the volatile composition of espresso and plunger coffees the polydimethylsiloxane coating was chosen. SPME/gas chromatography (GC)/mass spectrometry (MS) analyses allowed the identification of 37 compounds: four aldehydes, two ketones, 11 furans, 10 pyrazines, two pyridines, three phenolic compounds, two indoles, one lactone, one ester and one benzothiazine. The volatile composition was related more to the botanical variety (Arabica or Robusta) than to the method of preparation of the brew (espresso or plunger). Furthermore, use of the variability provided solely by the GC peak areas and respective retention times, combined with principal component analysis (PCA), yielded the information necessary for discrimination. The combined technique of headspace SPME/GC/PCA, as an alternative to conventional techniques based on GC/MS, is proposed as a lower‐cost, fast and reliable technique for the screening and distinction of coffee brews. Copyright © 2003 Society of Chemical Industry     

Authentication of Coffee Bean Variety by Near-infrared Reflectance Spectroscopy of Dried Extract

The potential of near-infrared (NIR) reflectance spectroscopy for discriminating between coffee beverage prepared from pure Arabica, pure Robusta and blends of these two varieties was investigated. Dried beverages were produced by both lyophilisation and air-drying under vacuum on glass-fibre filter paper. Spectral collections were treated by principal component and factorial discriminant analyses. Using the wavelength range 1100–2498 nm, only three of 65 test samples were misclassified when the filter paper approach was used. When freeze-dried coffee beverages were analysed, nine of the 65 test samples were misclassified. The basis for this discrimination appears to involve caffeine and/or other alkaloids.     

Profiles of volatile compounds and sensory characteristics of Robusta coffee beans roasted by hot air and superheated steam

Although superheated steam (SHS) roasting has proved to be capable of improving selected quality of roasted Robusta coffee beans, impact of SHS roasting on aroma characteristics of the beans is not well understood. This study therefore aimed to investigate the effect of SHS roasting on aroma profiles and sensory characteristics of Robusta beans undergone SHS roasting at 190–250 °C; results were compared with those of beans roasted by hot air (HA). Sensory characteristics of selected samples were also compared with HA-roasted Arabica beans. Forty five aroma compounds were identified; most were fully developed in beans roasted at 230 °C and tended to degrade in beans roasted at 250 °C. SHS roasting led to more extensive formation of aroma compounds contributing to caramel note, while helped reduce formation of major contributors to spicy, roasty and burnt notes. SHS-roasted Robusta beans exhibited more resemblance to Arabica beans than their HA-roasted counterpart.     

Optimization and Application of a HS-SPME-GC-MS Methodology for Quantification of Furanic Compounds in Espresso Coffee

A headspace solid-phase microextraction gas chromatography (GC)-mass spectrometry (MS) method previously optimized for analyses of volatiles in coffee was used for simultaneous quantification of major furanic compounds (2-furfural, furfuryl alcohol, 5-methylfurfural and furfuryl acetate) and furan, in espresso coffee prepared from hermetically closed capsules. High sensitivity was achieved with low limits of detection and limits of quantification. Good linearity was observed with correlation coefficients higher than 0.999. Recovery percentages were 102 % for furan, 99.7 % for 2-furfural, 98.0 % for furfuryl alcohol, 99.8 % for 5-methylfurfural and 99.9 % for furfuryl acetate. The method was applied to the analyses of espresso coffee from hermetically closed capsules. A total of 69 volatiles for Blend Roast and Blend Dark Roast samples, 64 volatiles for Arabica Dark Roast samples, 91 volatiles for Arabica Light Roast samples, 96 volatiles for Caramel coffee, 90 volatiles for Vanilla coffee and 92 volatiles for Almond coffee. In general, furanic compounds were the major chemical family, ketones, aldehydes, acids, pyrazines, pyrroles, alcohols, pyridines, aromatic compounds, hydrocarbons, and ethers were also detected. Total content of these furanic compounds varied from 105 to 199 μg ml^?1. The optimized method proved to be a reliable methodology for quantification of major furanic compounds and furan present in different types of espresso coffee. Although relative percentage of peak area is a good method for discriminate volatiles in different coffee brews with closer composition, the quantification of furanic compounds is more accurate for understand the real intake amount.     

Fungal colonization and biochemical changes in coffee beans undergoing monsooning

Changes in the mycofloral composition and concentrations of proteins, reducing sugars, phenols and tannins in coffee beans were analysed during different weeks of monsooning in Coffea arabica L. (Arabica) and C. canephora Pierre ex Froehner (Robusta). The highest fungal populations occurred during the fourth to seventh week of the monsooning process and the dominant fungal species were Aspergillus niger, Aspergillus tamarii, Aspergillus candidus, Penicillium spp. and Absidia heterospora. The protein and reducing sugar content increased steadily while the tannin content decreased beyond the detectable limit during monsooning. The phenolic content, however, was found to decline in the case of Robusta and increase slightly in Arabica. Throughout the study the monsooned coffee beans had different mycoflora and varied biochemical composition compared to non-monsooned coffee beans.     

Chemical characterisation of non-defective and defective green arabica and robusta coffees by electrospray ionization-mass spectrometry (ESI-MS)

The coffee roasted in Brazil is considered to be of low quality, due to the presence of defective coffee beans that depreciate the beverage quality. These beans, although being separated from the non-defective ones prior to roasting, are still commercialized in the coffee trading market. Thus, it was the aim of this work to verify the feasibility of employing ESI-MS to identify chemical characteristics that will allow the discrimination of Arabica and Robusta species and also of defective and non-defective coffees. Aqueous extracts of green (raw) defective and non-defective coffee beans were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS) and this technique provided characteristic fingerprinting mass spectra that not only allowed for discrimination of species but also between defective and non-defective coffee beans. ESI-MS profiles in the positive mode (ESI(+)-MS) provided separation between defective and non-defective coffees within a given species, whereas ESI-MS profiles in the negative mode (ESI(−)-MS) provided separation between Arabica and Robusta coffees.     

Changes on the levels of serotonin precursors – tryptophan and 5-hydroxytryptophan – during roasting of Arabica and Robusta coffee

The levels of free and total tryptophan and of 5-hydroxytryptophan (5-HTP) were investigated in green and roasted grains and beverages of Coffea arabica L. (Arabica) and Coffea canephora Pierre var. robusta (Robusta). Grains were light, medium and dark roasted. Free and protein tryptophan were extracted before and after hydrolysis. The levels of tryptophan and 5-HTP were quantified simultaneously by ion-pair HPLC and fluorimetric detection after derivatisation with o-phthalaldehyde. Robusta green coffee had higher total and protein tryptophan, whereas Arabica had higher free tryptophan levels. 5-HTP was not detected in the samples before and after roasting. Free tryptophan was completely degraded during roasting. Roasting significantly affected protein tryptophan. The rate of loss was smaller in Arabica compared to Robusta at every roasting degree. A beverage prepared the Brazilian way with a medium-roasted coffee provided 1.4–2.5 mg tryptophan/50 ml cup.     

Studies on acrylamide levels in roasting, storage and brewing of coffee

The content of acrylamide in coffee reaches a peak early in the roasting process, reflecting occurrence of both formation and destruction of acrylamide during roasting. Levels of acrylamide in the fully roasted product are a small fraction of the peak reached earlier. Glucose and moisture in green coffee do not show a significant correlation with acrylamide in roasted coffee. Pre-roasting levels of asparagine show a correlation only in Arabica coffee. The main factors affecting the level of acrylamide in roasted coffee appear to be the Arabica/Robusta ratio, with Robusta giving higher levels; time and degree of roast, with both shorter and lighter roasting at the edges of the normal roasting range giving higher levels; storage condition and time, with clear reduction at ambient storage. This storage reduction of acrylamide followed second order reaction kinetics with an activation energy of 73 KJ/mole. The acrylamide in roasted coffee is largely extracted into the brew and stable within usual time of consumption. As these four main factors also substantially affect the sensorial characteristics of the brew, and as modifications of the process have to comply with the consumer-accepted boundaries of taste profiles, only small effects on the acrylamide level are expected to be achievable.     

Application of Near-Infrared Hyperspectral Imaging with Variable Selection Methods to Determine and Visualize Caffeine Content of Coffee Beans

Hyperspectral imaging covering the spectral range of 874–1734 nm was used to determine caffeine content of coffee beans. Spectral data of 958.24–1628.89 nm were extracted and preprocessed. Partial least squares regression (PLSR) model on the preprocessed full spectra obtained good performance with coefficient of determination of prediction (R ² _p ) of 0.843 and root mean square error of prediction (RMSEP) of 131.904 μg/g. In addition, 10 variable selection methods were applied to select the best optimal wavelengths. The PLSR models on the different optimal wavelengths obtained satisfactory results. The PLSR model on the wavelengths selected by random frog (RF) performed the best, with R ² _p of 0.878 and RMSEP of 116.327 μg/g. The RF wavelength selection combined with the PLSR model also achieved satisfactory visualization of caffeine content between different coffee beans. The overall results indicated that optimal wavelength selection was an efficient method for spectral data preprocessing, and hyperspectral imaging was illustrated as a potential technique for real-time online determination for caffeine content of coffee beans.     

Profiles of volatile compounds and sensory analysis of three blends of coffee: influence of different proportions of Arabica and Robusta and influence of roasting coffee with sugar

One hundred and forty‐six volatile compounds were identified and quantified using a static headspace sampler in three blends of coffee: Arabica/Robusta 80:20 (A80:R20) natural roasted coffee, Arabica/Robusta 20:80 (A20:R80) natural roasted coffee and Arabica/Robusta 20:80 with 50% of Robusta coffee roasted with sugar (A20:R80 50% Torrefacto). The different proportion of Arabica and Robusta coffee in the blend A80:R20 versus A20:R80 influenced the amounts of 20 chemical families of volatile compounds. Aldehydes, ketones, alcohols, pyrroles, pyrazines, furans, thiazoles, thiophenes, esters, oxazoles, lactones, sulphur compounds, pyridines, alkanes, alkenes, phenolic compounds, benzenic compounds, acids, pyranones and terpenes were present in higher quantities in the sample containing 80% of Arabica coffee, whereas sulphur compounds were more abundant in the coffee with 80% of Robusta. Sensory differences were also found between the two blends of coffee in the burnt, caramel, nutty, earthy and roasty notes. Torrefacto coffee, widely consumed in Spain, is obtained by roasting coffee with sugar. Higher quantities of ketones, alcohols, pyrazines, furans, pyridines, alkanes, phenolic compounds, pyranones and terpenes were found in the blend A20:R80 50% Torrefacto coffee versus A20:R80 natural roasted coffee. These differences in the volatile fraction were perceived by our panellists in the intensities of the nutty, roasty, earthy, burnt and caramel notes. © 2002 Society of Chemical Industry