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Abstract
Coffee beans (arabica) with different degrees of roast were sequentially extracted with water (90 8C, 1 h), water (170 8C, 30 min), and
0.05 M NaOH (0 8C, 1 h). The amount and composition of polysaccharides, oligosaccharides and monosaccharides in the extracts and
residues were analyzed. The results were compared with the composition of the same batch of green arabica coffee beans. Although part of
our results were already reported in rather fragmented studies, this study gives a more complete overview of the amount and composition of
unextractable polymers, extractable polymers, oligomers, monomers, and their conversion into (non-sugar) degradation products as a
function of their degree of roast.
It was found that most carbohydrates in the roasted coffee bean were present as polysaccharides (extractable or unextractable). The fact
that only a small part of the carbohydrates in the extracts were recovered as oligomer and even less as monomers, showed that oligomers and
especially monomers were converted very rapidly into Maillard and pyrolysis products. Cellulose remains unextractable and its solubility
was not affected by the degree of roast. Galactomannans were also mainly present as unextractable polymers in green beans, but were
solubilized to a large extent with increasing degrees of roast. The arabinogalactans in the roasted bean were highly soluble at the extraction
conditions used. The arabinose as present as side-chains in the arabinogalactans were found to be more susceptible to degradation at more
severe roasting conditions than the galactans. Also evidence was found that populations of arabinogalactans with very different ara:gal ratios
exist in the roasted beans as well as in the green beans.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Arabica; Coffee beans; Roasting; Arabinogalactans; Galactomannans
1. Introduction
Roasting is an essential step in coffee production for
the formation of various types of flavour compounds. The
conversion of carbohydrates contributes significantly to
the formation of these compounds (Maria, Trugo, Moreira,
& Werneck, 1994; Steinhauser, Oestreich-Janzen, & Baltes,
1999). Two types of polysaccharides are the predominating
carbohydrates in coffee beans and extracts thereof: arabinogalactan type II and galactomannans (Fischer, Reimann,
Trovato, & Redgwell, 2001; Wolfrom, Plunkett, & Laver,
1960). The arabinogalactans consist of a main chain of
1 ! 3-linked galactose branched at C-6 with side-chains
containing arabinose and galactose residues (Fischer,
* Corresponding author. Fax: 31-317-484893.
E-mail address: henk.schols@wur.nl (H.A. Schols).
0144-8617/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0144-8617(03)00164-4
184
2. Experimental
2.1. Materials
Green Coffea arabica beans were roasted to a degree of
roast of 11% (Light), 15% (Medium), and 22% (Dark),
respectively (DR; expressed as the percentage of dry weight
loss of green coffee beans).
2.2. Extraction of polysaccharides from the roasted coffee
beans
Ground coffee beans were Soxhlet-extracted for 6 h with
petroleum ether to remove the lipids. Defatted ground coffee
beans (100 g) were sequentially extracted with 2000 ml of
water (90 8C, 1 h), water (170 8C, 20 min), and 0.05 M
NaOH 0.02 M NaBH4 (0 8C, 1 h). All extracts were
neutralized to pH 6, dialyzed, and freeze dried. The
monosaccharide content of the extracts was determined
before dialysis. The content of low molecular weight
material (LMWM; monomers plus oligomers) was determined by filtration over a 10 kDa filter membrane.
Subsequently, the filtrate was analysed.
2.3. Analytical methods
The uronic acid contents of the extracts were determined
by the automated m-hydroxy biphenyl assay (Thibault,
Rhamnose
Arabinose
Xylose
Mannose
Galactose
Glucose
Uronic acid
Total sugar (% w/w)
Degree of roast
Green
Light
Medium
Dark
1
10
1
42
24
18
6
46
0
1
7
1
48
23
15
5
42
11
1
6
1
51
22
16
4
41
15
1
5
1
51
21
18
4
37
22
185
water at 90 and 170 8C, and with 0.05 M NaOH (Table 2).
Although the amount of sugars extracted from the roasted
beans was comparable for light, medium, and dark roasted
coffee beans, the sugar composition of the polymeric
fraction varied significantly. The extractability of the sugars
had the following order: galactose . rhamnose . uronic
acid . arabinose . mannose . glucose. A major part of
the polysaccharides from the roasted arabica bean was
recovered in the residue: 45% for the dark roasted beans to
59% for the light roasted bean.
Extraction of light roasted coffee with water at 90 8C
beans yielded an extract consisting mainly of polysaccharides containing mannose (39 mol%) and galactose
(38 mol%). The mannose:galactose ratio of 1.0 was in
agreement with the results found by Leloup and Liardon
(1993) for a hot water extract obtained from roasted
coffee beans by extraction for 30 min at 95 8C. However,
Nunes and Coimbra (2003) found a ratio of mannose:galactose of , 0.55 for a 90 8C hot water extract. Also,
some arabinose (13 mol%) and galacturonic acid
(7 mol%) was present in the 90 8C extract. This sugar
composition indicates the presence of galactomannans,
arabinogalactans, and pectins. When comparing the
polymeric fraction of the 90 8C extract from the light
roasted coffee beans with those from the medium and
dark roasted coffee beans, a decrease of the relative
amount of arabinose, galactose, and galacturonic acid was
found for coffee beans with a higher degree of roast.
Also, the ratio arabinose:galactose decreased from 0.34
for the 90 8C extract from light roasted coffee beans to
0.24 for dark roasted coffee beans. The mannose content
increased significantly showing that the extractability of
the galactomannans in coffee beans increased with
increasing degree of roast. Extraction of light roasted
coffee beans with water at 170 8C yielded a polymeric
fraction with a high galactose content, indicating that it
contained mainly (arabino)galactans. This was in agreement with the results found by Leloup and Liardon (1993)
for extraction of roasted coffee beans for 15 min at
180 8C. In comparison with the 90 8C water extract the
ratio arabinose:galactose was much lower in the 170 8C
water extract (0.12 versus 0.34, respectively). Apparently,
arabinose is removed from the arabinogalactans at these
high extraction temperatures, or a different type of
galactan, containing less arabinose, is released.
In the polymeric fraction of the 170 8C extracts of the
medium and dark roasted coffee beans lower relative
galactose and arabinose contents were found in comparison to the light roasted coffee beans. In the extract from
the medium and dark roasted coffee beans the relative
mannose content was significantly higher when compared
to light roasted beans (0.24 versus 0.41 and 0.83,
respectively). The mannose:galactose ratio increased
from 0.24 for light roasted beans to 0.41 and 0.83 for
medium and dark roasted coffee beans, respectively.
Our results indicate that a darker degree of roast results
186
Table 2
Composition of the polymeric fraction of extracts obtained from roasted Arabica coffee beans
Sugar residues (mol%)
Rha
Ara
Xyl
Man
Gal
Glc
UA
Sugars (%w/w)
Yield (% w/w)
Light
Water, 90 8C
Water, 170 8C
0.05 M NaOH
Residue
2
0
0
0
13
8
8
1
0
0
0
1
39
16
18
67
38
67
63
2
1
0
1
27
7
8
10
2
51
65
25
59
4.6
5.2
0.5
23.6
9
8
2
40
Medium
Water, 90 8C
Water, 170 8C
0.05 M NaOH
Residue
1
0
0
0
10
7
7
1
0
0
0
1
43
25
27
66
38
61
57
2
1
1
1
28
7
7
7
2
54
67
25
57
4.9
4.7
0.8
20.5
9
7
3
36
Dark
Water, 90 8C
Water, 170 8C
0.05 M NaOH
Residue
1
0
0
1
8
5
6
1
0
0
0
1
51
40
30
60
33
48
51
3
2
1
6
34
5
7
7
1
51
56
20
53
5.6
3.9
0.6
17.5
11
7
3
33
Table 3
Sugar composition (mol%) and yields (g per 100 g roasted coffee) of LMWM from extracts obtained from roasted coffee beans
Rha
Ara
Xyl
Man
Gal
Glc
UA
Yield of LMWM
g/100 g beans
Light 90 8C
Light 170 8C
Light 0.05 M NaOH
2
1
0
17
24
21
1
0
0
30
26
27
28
38
30
7
2
0
16
10
21
2.0
2.4
0.7
Medium 90 8C
Medium 170 8C
Medium 0.05 M NaOH
2
1
0
18
22
16
0
0
0
24
31
39
34
32
31
6
2
0
16
12
14
1.8
1.8
0.8
Dark 90 8C
Dark 170 8C
Dark 0.05 M NaOH
1
1
1
9
16
12
0
1
1
40
45
38
38
27
33
5
2
3
8
9
13
3.0
2.5
1.0
187
Table 4
Free monomer composition (mol%) of extracts obtained from roasted Arabica coffee beans
Rha
Ara
Gal
Glc
Man
Xyl
Monomer yield
(mg/100 g beans)
Light 90 8C
Light 170 8C
Light 0.05 M NaOH
5
11
0
42
69
91
25
14
3
19
2
1
0
5
5
9
0
0
28
237
53
Medium 90 8C
Medium 170 8C
Medium 0.05 M NaOH
9
13
0
38
65
96
21
15
1
24
2
0
0
6
3
8
0
0
23
201
47
Dark 90 8C
Dark 170 8C
Dark 0.05 M NaOH
8
14
0
34
59
91
20
19
3
32
2
1
0
7
5
7
0
0
30
191
48
188
Gal
Glc
Man
3
4
6
4
9
12
15
22
39
36
40
42
23
2
3
7
27
47
36
26
Pool
Pool
Pool
Pool
I
II
III
IV
2
2
2
3
9
11
12
18
37
35
40
48
21
2
2
4
31
50
43
28
Dark
Pool
Pool
Pool
Pool
I
II
III
IV
1
1
2
2
5
6
8
13
40
28
34
37
8
3
3
4
45
61
53
43
3
0
0
0
4
9
12
12
76
85
71
63
9
0
0
0
8
6
17
25
Medium
Pool
Pool
Pool
Pool
I
II
III
IV
5
0
0
0
5
8
7
11
77
75
65
65
2
1
0
0
11
16
28
24
Dark
Pool
Pool
Pool
Pool
I
II
III
IV
0
0
0
0
3
5
4
5
77
57
48
46
4
1
3
4
17
36
46
45
5
0
4
3
6
4
22
27
33
36
70
57
0
0
0
0
55
60
4
12
Ara
Medium
Rha
Medium
Pool
Pool
Pool
Pool
I
II
III
IV
0
1
0
0
4
2
27
22
51
38
66
62
0
0
0
0
45
59
7
16
Dark
Pool
Pool
Pool
Pool
I
II
III
IV
0
0
0
0
8
10
8
11
45
63
80
68
0
0
3
0
47
26
8
21
into four pools, as shown in Fig. 3b. Galactose was the most
abundant sugar in pool I (Table 5b). The arabinose:galactose ratio was very low in this pool. Galactose was also the
most abundant sugar in pool II, III, and IV, but the arabinose
and mannose content increased with decreasing molecular
weight. Similar findings were found by Leloup and Liardon
(1993) and Leloup et al. (1997).
For the 0.05 M NaOH extracts a number of populations
could be distinguished (Fig. 3c): two high molecular weight
populations eluted at 19 and 21 min, as well as a population
which eluted at approximately 27.5 min, with a slight
shoulder at 30 min. The populations eluting at 19 and
189
Table 6
Percentage of individual sugars of light roasted coffee beans that was
recovered as unextractable polymer, extractable polymer, oligomer,
monomer, or that was converted into degradation products
Rha
Ara
Xyl
Man
Gal
Glc
UA
Total
6
20
17
3
0
13
8
5
0
61
0
6
0
56
6
100
3
24
13
10
1
23
7
13
3
55
0
4
1
44
7
100
32
5
3
2
1
3
2
1
0
6
1
0
0
52
9
100
54
12
9
4
0
7
3
3
1
0
0
0
0
6
21
100
3
48
15
31
3
14
5
8
2
0
0
0
0
27
8
100
64
1
1
0
0
2
2
1
0
0
0
0
0
24
10
100
13
30
13
16
2
26
12
9
5
36
21
30
2
100
19
13
100
4
20
12
7
1
17
7
8
3
44
0
3
1
51
8
100
29
5
2
2
1
1
1
0
0
4
4
0
0
54
11
100
49
15
10
5
1
6
2
3
2
1
0
0
0
12
17
100
3
42
16
23
3
12
5
5
20
3
0
0
0
32
12
100
67
1
1
0
0
2
1
0
0
0
0
0
0
21
10
100
10
25
12
12
1
22
10
8
4
35
19
43
0
100
24
14
100
2
14
9
4
1
16
5
8
2
4
0
2
1
66
3
100
30
4
2
2
1
7
0
4
2
0
0
0
0
58
2
100
34
21
13
7
1
12
6
5
2
0
0
0
0
28
5
100
3
33
15
15
3
17
9
5
3
0
0
0
0
47
0
100
68
2
2
0
1
3
2
1
0
0
0
0
0
27
0
100
5
22
11
9
1
20
8
8
5
28
14
59
25
100
38
7
100
16
16
13
2
0
12
6
4
2
6
0
5
0
61
24
100
11
4
5
1
13
The amount of the individual sugar in the green coffee bean is set to
100%. The weight loss during roasting was included.
190
A. Oosterveld et al. / Carbohydrate Polymers 54 (2003) 183192
Fig. 4. Recoveries of arabinogalactans (A), galactomannans (B), pectic backbone (C), and cellulose (D) as unextractable polymer (UE), extractable polymer (PS), oligomer (OS), monomer (MS), or degradation
products (De) as a function of the degree of roast. NA: not analysed.
191
4. Concluding remarks
The overview of the carbohydrates present in coffee
beans as a function of the degree of roast as given in this
investigation shows large differences for different types of
polysaccharides. In general it was found that depending on
the type of polysaccharide present in the green bean, most
carbohydrates were present as unextractable or extractable
polysaccharides. The fact that only very small amounts of
the carbohydrates were recovered as oligomer and even
less as monomers, shows that both oligomers and
monomers are converted very rapidly into sugar degradation products.
It was found that after removal of the water soluble
polysaccharides with water of 90 8C a large amount of
polysaccharides could be solubilized with water of 170 8C.
And the amount and composition of the material extracted
in this way clearly depended on the degree of roast. This not
only confirms that roasting solubilizes part of the polysaccharides, it also shows that the structure of the insoluble
polysaccharides is changed in such a way that they can be
extracted much easier when using more severe extraction
conditions.
Cellulose was found to be highly unextractable and not
affected by the degree of roast, while galactomannans were
also highly unextractable, but were solubilized to a large
extent with increasing degrees of roast. The arabinogalactans were found to have a high solubility, especially at
higher temperatures. For the first time evidence was found
that different populations of arabinogalactans exist in the
coffee bean; high molecular weight arabinogalactans with a
low arabinose substitution and low molecular weight
arabinogalactans with a higher arabinose substitution. The
arabinose side-chains in the arabinogalactans were found to
be more susceptible to higher roasting conditions than the
galactans.
With this study more insights have been obtained in the
structure of polysaccharides in coffee beans and
the degradation reactions, which occur as a function of the
degree of roast. While in previous manuscripts the
investigations towards the effect of roasting of coffee
beans focussed mainly on one distinct aspect of the
degradation reactions, in this paper we aimed to give a
more complete overview of the changes, which occurred in
all carbohydrate fractions during roasting.
192
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