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Food Chemistry 124 (2011) 863868

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Antioxidant activity, polyphenols, caffeine and melanoidins in soluble coffee:


The inuence of processing conditions and raw material
J.A. Vignoli a,*, D.G. Bassoli a, M.T. Benassi b
a
b

Companhia Iguau de Caf Solvel S.A., Research and Development Department, BR-369, Km 88, C.Procpio, PR, Brazil
Departamento de Cincia e Tecnologia de Alimentos, Centro de Cincias Agrrias, Universidade Estadual de Londrina, Rodovia Celso Garcia Cid, Km 6, Londrina, PR, Brazil

a r t i c l e

i n f o

Article history:
Received 1 December 2009
Received in revised form 28 June 2010
Accepted 2 July 2010

Keywords:
Coffea arabica
Coffea Canephora
Roasting degree
Extraction

a b s t r a c t
The production of soluble coffee starts with the selection of beans and is followed by roasting, grinding,
extraction and drying. Lyophilised soluble coffees extracted by various methods from light, medium and
dark-roasted arabica and robusta beans were evaluated for antioxidant activity (AA) using ABTS, Folin,
DPPH and FRAP techniques. Caffeine, chlorogenic acid (5-CQA) and melanoidin content was also quantied.
The data were analysed by principal component analysis. The AA values derived from the various methods
used were correlated. Roasting resulted in the degradation of 5-CQA and formation of melanoidins, while AA
was largely unaffected by roasting. The extraction of soluble coffee more prominently affected the AA of
light-roasted coffee, mainly because it favoured the extraction of 5-CQA. The larger caffeine content in
robusta coffee resulted in greater AA. All of soluble coffee products studied possessed antioxidant potential,
which was conferred by their concentrations of phenolic compounds, caffeine and melanoidins.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Coffee is a major commodity in the world economy, second only
to petroleum (Borreli, Visconti, Mennella, Anese, & Fogliano, 2002).
The most widely cultivated species are Coffea arabica (arabica) and
Coffea canephora (robusta). Despite the poorer sensory quality of C.
canephora, it has the advantage of allowing extraction of large
amounts of soluble solids, which enables its use in blends and in
the soluble coffee industry. Beverages prepared from roasted beans
have pleasant avour and aroma in addition to their physiological
effects. The preference for different kinds of coffee beverages is
strictly associated with social habits and country cultures. The
company GEA Niro (Parma, Italy), a traditional producer of process
lines for instant coffee and tea, reported that soluble coffee is
widely consumed (45% in Eastern Europe, 53% in Asia/Pacic, and
79% in Australia), standing out in countries where tea is a traditional beverage (GEA-Group Coffee, 2010). Soluble coffee exports
are a major source of revenue in Brazil due to the higher aggregate
value of the product (ABICS, 2008).
Recently, scientic studies have pointed out the positive effect of
coffee on human health (Coughlin, 2006). In general, recent studies
report little evidence of health risks and considerable evidence of
health benets for healthy adults as a result of moderate coffee consumption (Higdon & Frei, 2006). The beverage also stands out as a dietary source of potential antioxidants, such as caffeine (Devasagayam,
* Corresponding author. Tel.: +55 43 3401 1542; fax: +55 43 3524 2542.
E-mail address: jvignoli@iguacu.com.br (J.A. Vignoli).
0308-8146/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2010.07.008

Kamat, Monhan, & Kesavan, 1996; Shi & Dalal, 1991), chlorogenic
acids (Gmez-Ruiz, Lake, & Ames, 2007; Moreira, Monteiro, RibeiroAlves, Donangelo, & Trugo, 2005), hydroxycinnamic acids (Gallardo,
Jimnez, & Garcia-Conesa, 2006), and Maillard reaction products,
such as melanoidins (Borreli et al., 2002; Delgado-Andrade, RunHenares, & Morales, 2005). Thus, the antioxidant capacity of coffee
is related to the presence of both natural constituents and compounds
formed during processing. The antioxidant potential of coffee has
been evaluated by several methods, such as ferric reducing antioxidant power (FRAP), 2,20 -azinobis(3-ethylbenzothiazoline-6-sulphonic acid assay (ABTS), 2,2-diphenyl-1-picrylhydrazyl assay
(DPPH) and determination of total phenolics (Borreli et al., 2002; Snchez-Gonzalez, Jimnez-Escrig, & Saura-Calixto, 2005).
The FRAP method measures the ferric reduction of 2,4,6-tripyridyl-S-triazine (TPTZ). This reaction detects compounds with redox
potentials lower than 0.7 V (the redox potential of Fe3+-TPTZ). Assays
using the ABTS radical, including TEAC, are based on the ability of
antioxidants to scavenge the long-lived ABTS radical; using a similar
mechanism, the DPPH assay measures the reduction of the stable
radical 2,2-diphenyl-1-picrylhydrazyl by monitoring the decrease
in its absorbance at 515 nm. The FolinCiocalteau method has been
used for years to measure total phenolic compounds and is also useful in evaluating antioxidant activity (Benzie, 1996; Prior, Xianli, &
Schaich, 2005).
As compared to other beverages, coffee stands out for its antioxidant potential. Some authors have reported greater AA for soluble
and espresso coffee than those of red wine and green tea (Pellegrini
et al., 2003). AA is also affected by the green bean composition and

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J.A. Vignoli et al. / Food Chemistry 124 (2011) 863868

processing methods. Daglia, Papetti, Gregotti, Bert, and Gazzani


(2000) studied beverages made from different coffee beans and reported a greater antioxidant capacity for C. canephora than for C.
arabica. Del Castillo, Ames, and Gordon (2002) observed a decrease
in AA that was correlated with the degree of roasting, associated
mainly with the degradation of chlorogenic acid. In contrast, the
roasting process can also contribute to the formation of melanoidins, which have already been reported to be responsible for AA
in high molecular weight fractions isolated from roasted coffee
(Daglia et al., 2000).
Most studies in literature refer to the AA of roasted coffee. Despite the great economic importance of soluble coffee, little has
been reported about its antioxidant potential or the inuence of
processing conditions. To become solubilised, coffee undergoes
an extraction process. The beans are roasted, ground and subjected
to successive percolation with water at temperatures ranging from
100 to 180 C. Chemically, percolation results in the selective solubilisation of coffee solids. Depolymerisation and degradation may
occur during high-temperature extraction (Leloup, 2006), and process variations may affect the products characteristics.
Thus, the objective of this study was to evaluate the effect of soluble coffee processing conditions (roasting and extraction method), as
well as the effect of raw materials (C. arabica andC. canephora species),
on the antioxidant capacity of coffee as measured by different techniques. In addition, representative compounds of the main classes
of antioxidants in soluble coffees (5-CQA, caffeine and melanoidins)
were analysed allowing to explain the variations observed in AA.

2. Materials and methods


2.1. Materials and samples
Coffee samples were provided by Companhia Iguau de Caf
Solvel (Cornlio Procpio, Paran State, Brazil) and were representative of different degrees of roasting, extraction conditions,
and raw materials.
Arabica (A) and robusta (B) coffee beans were roasted in a pilot
80-kg/h Rayar roaster for 710 min at 214225 C to obtain light
(L), medium (M), and dark (D) roasted beans, corresponding to
lightness values (L*) of 33, 25, and 14, respectively. Lightness
was assessed in triplicate with a Byk Gardner GmbH colorimeter
(Germany) with 45/0 geometry and CIE illuminant D65. Coffee
beans were ground to obtain adequate particle size for later processing as follows: 30% retention in a 4-mm sieve, 60% retention
in a 2-mm sieve and 10% retention in a 1-mm sieve.
The samples were extracted by two processes: conventional (1)
and double-extraction systems (2). Generally, a set of extraction
columns is lled in sequence and extracted with heated water. In
the conventional process (1), water at 180 C is fed into the rst
stage (column with older coffee) and subsequently percolated in
the following stages until it reaches newer coffee. In the last stage,
the extract reaches the newly added coffee and extracts its soluble
solids, preserving the aroma and avour. During the process, the
amount of soluble solids in the extract increase, while the temperature decreases. The fresh coffee is extracted in the last column at
approximately 100 C to minimise thermal damage. The resulting
extract is then lyophilised. In the double-extraction system (2),
one batch is fed into the selected stages at mild temperature and
pressure, which results in a better quality extract. A second batch
is fed into the remaining stages at higher temperature and pressure
to increase solubilisation. A mixture of 50% of the extracts from
each stream was lyophilised.
Antioxidant activity was determined by directly dissolving suitable concentrations of samples in water. All samples were prepared in duplicate and measurements were made in triplicate.

2.2. Chemical and equipments


5-O-Caffeoylquinic acid (5-O-CQA), caffeine and gallic acid (HPLC
grade) were purchased from SigmaAldrich (St. Louis, MO, USA).
ABTS (2,2-azinobis-3 ethyl benzothiazoline-6-sulphonic acid) and
DPPH (2,2-diphenyl-1-picrylhydrazyl) were obtained from Sigma
Chemical CO. (St. Louis, MO, USA). Trolox (6-hydroxy-2,5,7,8,tetramethylchromane-2-carboxylic acid) and TPTZ (2,4,6-tri(2-pyridyl)-S-triazine) were obtained from Fluka/SigmaAldrich (Vallensbaek Strand, Nordic, Denmark). FolinCiocalteau, acetic acid and
acetonitrile were purchased from Merck (Darmstadt, Hessen,
Germany).
Melanoidins were separated by dialysis using 1214 kDa cutoff
membranes (Spectra/Por, Irving, TX, USA).
AA measurements were taken in a UVVisUV mini-1240 spectrophotometer (Shimadzu, Kyoto, Japan) and bioactive compounds
were detected by HPLC. The HPLC apparatus consisted of a Dionex
LC (Idstein, Hesse, Germany) equipped with a P680 gradient pump,
TCC-100 column oven, automated sample injector (model ASI-100)
and photodiode array detector (model PDA-100). The system is
operated by computer using Chromeleon version 6.6 software.
2.3. Determination of antioxidant activity
2.3.1. ABTS methodology (TEAC)
Antioxidant capacity was estimated in terms of radical scavenging activity using the procedure described by Snchez-Gonzalez
et al. (2005). Briey, ABTS radical cations (ABTS+) were produced
by reacting 7 mM ABTS stock solution with 2.45 mM potassium
persulphate and allowing the mixture to stand in the dark at room
temperature for 1216 h before use. The ABTS+ solution (stable for
2 days) was diluted with 5 mM phosphate buffered saline (pH 7.4)
to an absorbance of 0.70 0.02 at 730 nm. After addition of 10 lL
of sample or trolox standard to 4 mL of diluted ABTS+ solution,
absorbance readings were measured after 6 min using a UVVis
1240 Shimadzu spectrophotometer. Ethanol solutions containing
known concentrations of trolox, a water-soluble analogue of vitamin E, were used for calibration. Results were expressed g of trolox
per 100 g of coffee (dry matter).
2.3.2. FRAP methodology
In FRAP experiments, the reduction power of various coffees
was estimated according to the procedure described by SnchezGonzalez et al. (2005). The FRAP reagent was prepared by mixing
of 2.5 mL of a 10 mM TPTZ solution in 40 mM HCl and 2.5 mL of
20 mM FeCl36H2O with 25 mL 0.3 mM acetate buffer pH 3.6. This
solution was incubated at 37 C for 30 min.
Approximately 900 lL of freshly prepared FRAP reagent,
warmed at 37 C, was mixed with 90 lL distilled water and either
10 lL of test sample or standard or appropriate reagent blank to
measure AA. After 30 min at 37 C, readings at the absorption maximum (595 nm) were taken. Ethanol solutions containing known
trolox concentrations were used for calibration. Results were expressed g of trolox per 100 g of coffee (dry matter).
2.3.3. DPPH methodology
The DPPH assay has been widely used to evaluate the ability of
several free radical scavenger molecules. DPPH assays were performed according to the procedure described by Casagrande et al.
(2007). Briey, solutions of coffee were prepared to obtain 2, 3, 4,
6, 10 and 15 mg/mL. One millilitre of 100 mM acetate buffer (pH
5.5), 1 mL of ethanol and 0.5 mL of 250 lM ethanolic DPPH solution were mixed and 10 lL of each sample of the above prepared
solutions were added. After 10 min, absorbance was measured at
517 nm. A positive control was prepared in the absence of coffee
solutions, which indicates the maximum amount of free DPPH

J.A. Vignoli et al. / Food Chemistry 124 (2011) 863868

(considered 100% of free radicals in the solution), to calculate the


hydrogen-donating ability (IA%) of coffee. The blank was prepared
from the reaction mixture without DPPH solution (Eq. (1)). The
IC50 (the concentration of substance that provides 50% reduction
of free radical concentration) was determined

IA % 100  Abs sample=Abs control  100

2.3.4. FolinCiocalteau methodology


Total polyphenol content was evaluated using the FolinCiocalteau reagent following a method adapted from Singleton, Orthofer,
and Lamuela-Raventos (1999). The sample (0.1 mL) was diluted
with deionised water to a volume of 7.5 mL. Then, 300 lL of
0.9 mol/L. FolinCiocalteau (FC) reagent and 1 mL of 20% Na2CO3
solution were added and deionised water was added up to a nal
volume of 10 mL. Solutions were maintained at room temperature
for 60 min and total polyphenol content was determined at
765 nm using a UVVis 1240 Shimadzu spectrophotometer. Gallic
acid standard solutions were used for calibration. The results were
expressed as g equivalents of gallic acid per 100 g of coffee (dry
matter).
2.4. Determination of the bioactive compounds of soluble coffee
2.4.1. Determination of 5-caffeoilquinic acid (5-CQA) and caffeine
High performance liquid chromatography (HPLC) was used to
determine 5-CQA and caffeine content (Alves, Dias, Scholz, & Benassi, 2006) using a 4.6  250 mm, 5 lm particle Spherisorb ODS2
column (Waters, EUA). Compounds were eluted with gradients
containing 5% acetic acid (A) and acetonitrile (B) as follows: 0
5 min: 4% B; 510 min: 10% B; 1030 min: 10% B; 3040 min: 0%
B; 4050 min: 4% B at a ow rate of 0.7 mL/min. Caffeine was detected at 272 nm while 5-CQA was detected at 320 nm. Quantication was carried out by external standardisation using a 5-point
calibration curve with triplicate measurements: the concentration
of 5-CQA ranged from 5 to 30 lg/mL while that of caffeine ranged
from 10 to 50 lg/mL. The samples were dissolved in ultra pure
water and passed through 0.22-lm lters directly into the chromatographic system.
2.4.2. Determination of melanoidins
A dialysis membrane separation system with a size exclusion
limit of 1214 kDa was used as described by Bekedam, Schols, Boekel, and Smit (2006), with modications. A soluble coffee solution
(20 mL) with a concentration of 45% was prepared. The solution
was transferred to the membrane and placed in a beaker with
400 mL distilled water under agitation. The water was changed
every 8 h until it was colourless. The material retained on the membrane was lyophilised and used to estimate the mass of the material
with molecular weight over 1214 kDa in relation to the initial mass.
This fraction, here considered to be melanoidin, was expressed as g
of melanoidins/100 g of sample.
2.5. Statistical analysis
Antioxidant activity and chemical composition results were
subjected to principal components analysis by the multivariate
exploratory techniques and principal components and classication analysis procedures using the Statistica 7.0 software package
(STATSOFT, So Caetano do Sul, Brazil).
3. Results and discussion
Soluble coffee beverages were assayed for their antioxidant
activity by monitoring their reaction with ABTS cation, their reduc-

865

ing capacity by the FRAP method and their capacity to scavenge


DPPH free radicals. Total phenolic compound content (FolinCiocalteau) was also determined (Table 1). Coffee compounds related
to antioxidant capacity, such as caffeine, 5-CQA and melanoidins,
were also quantied (Table 2).
Principal component analysis was used to evaluate the correlation between antioxidant activity and the chemical composition of
the various products. The rst two components (CP1 and 2) explained 87% of the total variance.
CP1 was determined by the antioxidant activity of the beverage
and its caffeine content, which was stable during the thermal process (Fig. 1A). It is important to note that all methods used gave
similar antioxidant activity results for each the samples, despite
their differing underlying mechanisms (Table 1).
The Folin method was highly correlated with the other methods
used (Fig. 1A). This assay determines the total polyphenol content
of a substance based on a redox reaction, thus it can be considered
an evaluation of antioxidant activity (Prior et al., 2005). In a study
of the inuence of coffee preparation methods on antioxidant activity, Snchez-Gonzalez et al. (2005) also observed a correlation between the polyphenol content determined by the Folin method
and FRAP values. In this work, the strongest correlation was found
between the Folin and the DPPH methods (r = 0.88), which suggests
scavenging of this radical by phenolic compounds. It is important to
note that DPPH values are represented as IC50; smaller values of IC50
correspond to higher AA values. Furthermore, the Folin results may
also be related to the reducing capacity of the coffee beverage, which
was evaluated by the FRAP method (r = 0.72) and ABTS radical
scavenging (r = 0.82).
CP2 correlated the 5-CQA and melanoidin contents, compounds
that are degraded or produced during the roasting process. A negative correlation was observed between these compounds; that is,
the concentration of high molecular weight compounds increased
concurrently with a decrease in 5-CQA content. No correlation
was observed between the concentrations of 5-CQA or melanoidins
and the AA results (CP1). The AA of the light and dark-roasted samples was similar (Tables 1 and 2, Fig. 1A).
Thus, PCA separated the samples by AA (CP1) and/or roasting
(CP2) (Fig. 1B). The lower two quadrants show a distinct group
formed by dark samples, independent of the raw material or the
extraction methods used. In the higher quadrants are the light
and medium roasting samples, with the robusta coffee on the left
(larger AA) and the arabica coffee on the right.
Considering the inuence of the raw material on AA, in general,
C. canephora samples yielded greater AA than the C. arabica samples (Table 1, Fig. 1B). Similar results, commonly attributed to
the larger CGA content of robusta coffee, were reported in other
studies of roasted coffee (Daglia et al., 2004). Nevertheless, this
study shows that isomer 5-CQA was present in similar or higher
concentrations in soluble arabica coffee than in robusta coffee (Table 2). According to Leloup (2006), although green robusta beans
have a higher CGA content, around 10% versus 8% in arabica coffee,
these compounds seem to be more sensitive to the roasting process
in a robusta coffee matrix. Clifford (1997) reported that for a similar degree of roasting, robusta coffee undergoes a larger absolute
loss of CGA, producing volatile phenols and guaiacol. Trugo and
Macrae (1984) and Dias (2005) also described a similar behaviour
for arabica and robusta coffees with different degrees of roasting.
Thus, the greater antioxidant capacity of robusta coffee could be
attributed to its higher caffeine content (Table 2), since it correlated positively with AA (Fig. 1). In a study of brewing procedure
inuence, Lopez-Galilea, De Pena, and Cid (2007) also reported a
signicant correlation between caffeine content and AA results obtained by DPPH (r = 0.83) and redox potential (r = 0.84). Parras,
Martinez-Tom, Jimnez, and Murcia (2007) evaluated the antioxidant activity of coffee from different origins in beverages prepared

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J.A. Vignoli et al. / Food Chemistry 124 (2011) 863868

Table 1
Antioxidant activity of soluble coffee obtained from different species and processing conditions evaluated by assorted methods.*

Assays

Roasting degree

Arabica

Robusta

Extraction 1

Extraction 2

Extraction 1

Extraction 2

ABTS (g trolox/100 g)

Light
Medium
Dark

18.77 1.00
21.03 2.25
23.78 0.25

23.27 0.00
23.53 0.75
24.78 0.00

27.28 0.25
36.05 1.75
33.93 1.50

32.29 3.25
32.79 0.50
27.79 3.75

FRAP (g trolox/100 g)

Light
Medium
Dark

19.27 2.25
25.03 0.50
27.78 0.25

25.03 0.00
30.79 0.50
26.03 0.50

26.28 1.50
34.04 0.75
35.04 0.75

29.78 0.50
34.54 1.00
29.78 1.75

Folin (g gallic acid/100 g)

Light
Medium
Dark

12.08 0.51
13.09 0.17
13.44 0.00

14.97 0.17
15.14 1.02
13.10 0.34

14.97 0.00
16.67 0.34
15.82 0.17

18.54 0.51
17.35 0.34
13.44 0.34

DPPH IC50 (lg/mL)

Light
Medium
Dark

24.92 0.55
19.87 1.38
20.51 0.18

16.11 0.26
18.80 0.47
20.23 1.02

16.35 0.34
16.14 0.11
16.79 1.04

14.81 0.37
14.70 0.20
19.47 0.35

Average of six measurements (duplicate in three repetitions) standard deviation.

Table 2
Contents of 5-CQA, caffeine, and melanoidins of soluble coffee obtained from different species and processes.*
Roasting degree

Arabica

Robusta

Extraction 1

Extraction 2

Extraction 1

Extraction 2

5-CQA (g/100 g)

Light
Medium
Dark

3.53 0.02
1.87 0.13
0.62 0.03

4.11 0.11
2.55 0.03
0.40 0.03

2.79 0.06
1.71 0.04
0.21 0.03

4.24 0.05
2.26 0.11
0.25 0.03

Caffeine (g/100 g)

Light
Medium
Dark

2.84 0.00
3.07 0.36
3.64 0.04

3.44 0.05
4.12 0.35
3.34 0.15

3.98 0.08
5.82 0.11
4.75 0.11

5.33 0.02
5.54 0.14
4.88 0.64

Melanoidins (g/100 g)

Light
Medium
Dark

23.80 0.77
18.07 0.45
29.64 1.59

20.13 0.59
22.08 0.04
25.42 0.01

27.30 0.51
19.66 2.04
30.44 1.84

22.89 0.38
21.28 1.65
26.50 0.19

Average of two measurements standard deviation.

5-CQA

1,0

(A)

(B)

3
2

FOLIN

PC 2 : 26%

PC 2 : 26%

0,5

0,0
CAFFEINE

ABTS
FRAP

DPPH

1
0

R E2 M
R E1 M

R E1 L

-1

A E2 M

A E1 M

A E1 L

A E2 D
A E1 D

R E2 D
R E1 D

-2

-0,5

A E2 L

R E2 L

-3

MELANOIDINS

-1,0
-1,0

-0,5

0,0

0,5

-4
1,0

PC 1 : 61%

-4

-3

-2

-1

PC 1 : 61%

Fig. 1. Principal component analysis of antioxidant activity and composition of soluble coffee: variable projection (A) and scatter plot for the samples (B). Species: (A) arabica
and (R) robusta. Extraction process: conventional (1) and double extraction (2). Roasting degree: light (L), medium (M), dark (D).

by different procedures (espresso, italian, and brewed) and found


higher TEAC values for caffeinated products than in decaffeinated
products.
Regarding the inuence of roasting on AA, it is worth noting
that there is little agreement in the literature, even for roasted coffee, which has been the most extensively studied. Del Castillo et al.
(2002) observed greater AA in medium-roasted coffee. Duarte,
Abreu, Menezes, Santos, and Gouva (2005) found greater AA for
beverages made from light-roasted coffee. In contrast, Nicoli,

Anese, Manzocco, and Lerici (1997) reported greater AA for


medium and dark-roasted coffee beverages. No reports are available on soluble coffee; however, it must be taken into account that
for soluble coffee, after roasting, there is an additional thermal
extraction treatment at high temperature.
The degree of roasting showed little inuence on the AA of soluble
coffees. Compounds that were affected by roasting (5-CQA and
melanoidins) are not directly related to the antioxidant potential
of the beverages. This may initially seem contradictory, given the

J.A. Vignoli et al. / Food Chemistry 124 (2011) 863868

acknowledged antioxidant activity of these compounds. Moreira


et al. (2005) described a strong correlation between the chlorogenic
acid content and the FRAP method, especially for caffeoylquinic isomers. Borreli et al. (2002) evaluated AA and the melanoidin content
of green and roasted coffee (light, medium and dark roast). The ABTS
method yielded AA values for all fractions: low (1.03.0 kDa), medium, and high molecular weight (over 100 kDa); however, the high
weight fractions that contained melanoidins and the low weight
fractions rich in phenolic compounds were the most active. Daglia
et al. (2004) obtained similar results for roasted coffee, correlating
AA and hydroxyl radical scavenging capacity. The authors reported
that high molecular weight fractions of green coffee were also evaluated; however, they did not present AA, which demonstrates that
roasting is responsible for the formation of AA compounds.
Frequently, studies of coffee AA available in the literature are
either restricted to just one roasting degree or focused on a specic
class of compounds (CGAs, caffeine, or melanoidins). A broader
analysis of these products as a function of roasting conditions,
extraction processes, and composition proles showed that the nal AA of coffee beverages results from the balance of degraded
and newly formed compounds during roasting. Increasing roasting
will degrade 5-CQA and will form high molecular weight polymers,
ensuring antioxidant activity remains unaffected by roasting conditions. In conclusion, under the conditions presently studied,
these two compounds contribute equally to AA. Furthermore, the
reduction of one is balanced by the formation of the other, which
explains the similar AA values found for light and dark-roasted coffees. Thus, we can conclude that AA depends more on coffee composition than on roasting degree.
In relation to the soluble coffee extraction process, the results of
the processes studied varied according to roasting degree (Table 2).
Both the arabica- and the robusta-derived products presented higher 5-CQA contents for light and medium-roasted coffee in the double-extraction system (2). Interestingly, this process also favoured
the extraction of caffeine from the two light-roasted coffee species;
only arabica was favoured by medium roasting. The extraction process of dark-roasted coffee did not inuence the release of these
compounds. It is likely that, after the matrix is extensively damaged by the roasting process, the extraction of compounds is easier
and occurs more or less independently of which process is used. In
the case of the robusta coffee matrix, which was more sensitive to
degradation, this behaviour was observed for some compounds even
in medium-roasted coffee.
Although the double-extraction process increased both the caffeine and 5-CQA content of the light-roasted nal product, this increase probably occurred in a different way for each compound.
The 5-CQA is a thermolabile compound and was probably preserved
in the rst extraction stream at milder temperatures. As caffeine is
thermostable, the double-extraction process may have released a
larger amount of compounds from the light-roasted matrix. Concerning the behaviour of melanoidins, in general, their extraction
was favoured by the single-extraction process. Both the contents
and the composition of the higher molecular weight fraction, considered to be melanoidins, are inuenced by the roasting process and
extraction conditions. As the molecular weight increases with the
thermal treatment, severe conditions also result in the degradation
of these compounds. Leloup (2006) evaluated the inuence of temperature on the molecular weight prole of carbohydrates and observed the formation of mono- and disaccharides with increasing
extraction temperature; however, under mild conditions, molecules
of over 10 kDa were formed. As two water streams are used in the
double-extraction process, one with a higher temperature, compounds with higher molecular weights are probably degraded.
More 5-CQA and caffeine were extracted by the double-extraction process, increasing the AA of the light-roasted product. This
demonstrates the effect of 5-CQA concentration on AA. For less in-

867

tense roasting systems, a process that yields higher concentrations


of 5-CQA is more advantageous. As this compound degrades and
the content of melanoidin increases, the extraction process has less
of an effect on AA.
Soluble coffee beverage thus possesses excellent antioxidant
potential, since its fabrication traditionally uses large amounts of
robusta coffee and the extraction processes favour the enrichment
of components with antioxidant potential, such as 5-CQA and
caffeine.
4. Conclusion
All of the studied soluble coffee products possessed antioxidant
potential conferred by balanced concentrations of phenolic compounds, caffeine and melanoidins. AA was unaffected by roasting
conditions, since the degradation of 5-CQA was balanced by the
formation of melanoidins. The extraction process had a greater
inuence on AA in lighter-roasted coffees. The higher caffeine content of C. canephora resulted in products with greater AA, indicating that the antioxidant activity of the nal product depends
mainly on the species used in blends.
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