Beruflich Dokumente
Kultur Dokumente
Chemistry
Food Chemistry 89 (2005) 427440
www.elsevier.com/locate/foodchem
Abstract
This study focuses on the impact of anthocyanin structures such as 5-glucosidic substitution and aromatic acylation on anthocyanin, colour and stability at various pH values. Two concentrations (0.05 and 0.15 mM) of cyanidin 3-glucoside (1), cyanidin
3-(200 -glucosylglucoside)-5-glucoside (2), and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) in aqueous
solutions were studied at fourteen pH levels between 1.1 and 10.5 during a 98 day period at 10 C. The three pigments represent the
structural variation of many anthocyanins isolated from fruits and vegetables. Colours were expressed by the CIELAB coordinates
hab , (hue angle), C (chroma saturation), and L (lightness), as well as by visible absorption maxima (kmax ) and molar absorption
coecients (e). Limitations of using only spectral parameters, such as kmax and e, to express colour variations, were revealed.
Pigment 2 was more unstable than 1 at most pH values, showing lower C and higher L values after storage for only hours in
neutral and weakly acid solutions. Pigment 3 showed higher colour stability than the nonacylated forms at all pH values but pH 1.1,
where all pigments retained their colours in the storage period, and in the most alkaline solutions, where all pigments experienced
dramatic colour changes. Of potential importance for some food products, in solutions with pH 4.1 and 5.1, 3 maintained nearly the
same hab , C , and L values during the whole measuring period (98 days), in contrast to pigments 1 and 2. The hue angle shift
towards bluish tones in freshly made samples of anthocyanins with 5-glucosidic substitution, were amplied with aromatic acylation
(3) throughout the entire pH range except pH 10.5. The variations in the results emphasizes the importance of structure for
anthocyanin properties in fresh and processed fruits and vegetables.
2004 Elsevier Ltd. All rights reserved.
Keywords: Anthocyanins; Colour; Stability; CIELAB; NMR
1. Introduction
Anthocyanins provide colours ranging from salmonpink through red, and violet to nearly black in a variety
of plant sources. They play a critical role in the colour
quality of many fresh and processed fruits. The interests
in and motives for extended use of these colorants are
inuenced by their potential benecial health eects
(Cliord, 2000). It is well known that anthocyanin
properties, including colour expression, are highly inuenced by anthocyanin structure and pH, etc. (Cabrita,
Fossen, & Andersen, 2000; Francis, 1989; Jackman,
Yada, Tung, & Speers, 1987). However, precise
0308-8146/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2004.03.002
428
for 98 days. The anthocyanins include cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside
(2) and cyanidin 3-(200 -(6000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3), which are representative
of the structural variation of most anthocyanins found
in fruits and vegetables (Mazza & Miniati, 1993). Thus,
it has been possible to compare under various pH conditions, especially the impact of 5-glucosidic substitution
and aromatic acylation, for colour, solubility and stability. The results vary tremendously, and this emphasizes the importance of structure on anthocyanin
properties in fresh and processed fruits and vegetables.
429
Table 1
1
H and 13 C spectral data for 1, 2 and 3 dissolved in CD3 OD:CF3 COOD (19:1) at 25 C
Aglycone
2
3
4
5
6
7
8
9
10
10
20
30
40
50
60
1, 1 H d (ppm)
1,
13
C d (ppm)a
2, 1 H d (ppm)
13
C d (ppm)a
3, 1 H d (ppm)
3,
13
C d (ppm)a
7.15 d; 8.9
8.35 dd; 8.7, 1.8
165.05
146.26
135.87
157.08
105.74
169.46
97.44
156.80
113.21
121.11
118.71
147.58
156.51
117.77
129.10
7.11 d; 8.7
8.30 d br; 8.4
163.85
145.29
134.16
156.2
105.42
169.08
97.06
156.2
112.67
120.85
117.93
147.44
156.52
117.28
129.54
5.58
4.17
3.88
3.60
3.72
4.04
3.84
d; 7.4
t; 8.2
t; 8.8
m
m
d br; 12.1
dd; 12.1, 5.4
102.40
81.63
78.08
70.97
78.68
62.4c
62.4c
5.74
4.24
3.93
3.81
3.97
4.64
4.46
100.25
79.65
76.49
71.08
75.14
63.37
63.37
200 -glc
1000
2000
3000
4000
5000
6000
4.89
3.29
3.39
3.32
3.05
3.57
d; 7.6
m
m
t; 9.3
m
m
104.55
75.79
77.70
71.26
77.96
62.4c
5.33d
4.97 t; 8.7
3.74 m
3.54e m
3.46e m
3.97 m
99.91
74.91
75.92
70.91e
78.05e
62.48
5-glc
10000
20000
30000
40000
50000
6A0000
6B0000
5.26
3.78
3.66
3.55
3.68
4.04
3.84
d; 7.8
t; 8.8
t; 8.8
m
m
d br; 12.1
dd; 12.1, 5.4
102.61
74.50
77.68
71.12
78.62
62.4c
62.4c
5.25 d; 7.5
3.83 m
3.65f m
3.53 m
3.66f m
4.03 m
3.78 m
102.39
74.52
77.68f
70.99
78.58f
62.27
62.27
3-glc
100
200
300
400
500
6A00
6B00
600 -sin
C@O
a
b
1
2
3
4
5
6
OMe
2000 -sin
C@O
a
b
1
2
3
4
5
6
OMe
9.04 s
6.75 s
6.98 s
8.11 s br
7.09 d; 8.2
8.32 d br; 7.9
5.39
3.77
3.67
3.54
3.65
4.01
3.81
d; 7.4
t; 8.0
t; 8.7
d; 11.8
dd; 12.2, 6.0
164.20
145.53
136.60
159.09
103.31
170.31
95.15
157.48
113.22
121.08
118.25
147.27
155.67
117.37
128.29
2,
103.58
74.71
78.01
71.01
78.68
62.29
9.16 s
7.14 s
7.17 s br
8.13 d; 1.8
8.85 s
7.01 s
6.71 s
7.85 s br
d; 6.1
t; 7.2
m
m
m
d br; 11.4
dd; 11.8, 4.5
6.22 d; 15.9
7.34 d; 15.9
6.60 s
6.60 s
3.80 s
6.29 d; 15.9
7.42 d; 15.8
6.66 s
6.66 s
3.85 s
168.42
115.00
146.94
125.80
106.51
148.92
139.44
148.92
106.51
56.56
167.91
115.41
147.08
126.00
106.38
149.09
139.40
149.09
106.38
56.55
430
Table 1 (continued )
See Fig. 1 for structures.
s:singlet; d:doublet; t:triplet; m:multiplet; br:broad. For some signals, the coupling constant(s) (in Hz) are presented after the multiplicity.
a 13
C chemical shifts for 1 and 2 were achieved from CAPT spectra. Heteronuclear NMR techniques (HSQC and HMBC) were used for shift
assignments of 3.
b
Weak signal.
c
The 13 C shifts of the three glucosyl C6 were almost identical.
d
Hidden under the solvent peak. The 1 H chemical shift was found from the HSQC spectrum.
e
Signals with the same superscript may be reversed.
f
Signals with the same superscript may be reversed.
HO
OH
OCH3
OH
2''
OCH3
2'''
OH
OH
OH
OH
HO HO
6''
OH
O
OCH3
H3CO
OH
Fig. 1. The structure of cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside, 3. Pigment 2, cyanidin 3-(200 -glucosylglucoside)-5-glucoside, is without the two sinapoyl groups.
431
Table 2
Solvent proportions (v/v) used in the buer solutions
pH
1.1
3.0
4.1
5.1
6.0
6.6
6.8
6.9
7.2
7.3
8.0
8.9
9.9
10.5
271.7
728.3
691.6
998.0
688.7
308.4
2.0
311.3
100.7
247.0
309.4
367.9
409.7
438.8
899.3
753.0
690.6
632.1
590.3
561.2
290.8
84.2
709.2
915.8
732.1
267.9
75.8
924.2
A: 0.2 M KCl, B: 0.2 M HCl, C: 0.1 M KHC8 O4 H4 , D: 0.1 M HCl, E: 0.1 M NaOH, F: 0.1 M KH2 PO4 , G: 0.025 M borax, H: 0.05 M Na2 HPO4 .
20
0
-20
10
hab
-40
-60
-80
-100
-120
-140
-160
pH
Lambda, max
(b)
640
620
600
580
560
540
520
500
1
11
pH
Fig. 2. (a) hab , values of freshly made 0.05 mM solutions of cyanidin 3-glucoside (1) (s), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) (M) and
cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) () at pH-values from 1.1 to 10.5. (b) kmax values of freshly made 0.05
mM solutions of cyanidin 3-glucoside (1) (s), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) (M) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 sinapoylglucoside)-5-glucoside (3) () at pH-values from 1.1 to 10.5.
80
70
60
50
C*
40
30
20
10
0
1
11
pH
Fig. 3. C values of freshly made 0.05 mM solutions of cyanidin 3glucoside (1) (s), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) (M)
and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) () at pH-values from 1.1 to 10.5.
Table 3
Absolute molar absorptivities, e (l/(mol cm)) for 0.05 mM cyanidin 3glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and
cyanidin
3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5
pH
1.1
3.0
4.1
5.1
6.0
6.6
6.8
6.9
7.2
7.3
8.0
8.9
9.9
10.5
16520
12240
5920
3540
8120
8340
8360
8620
8600
9180
8340
8020
8240
14380
19260
6060
1620
760
7740
12120
13340
15180
17640
19340
16220
16740
14420
20420
23460
22380
16360
9680
12380
12960
13260
16260
18140
20960
20820
20000
15080
15340
25000
Molare absorptivity
(l/(mol*cm))
432
20000
15000
10000
5000
0
1
11
pH
into account the absorption/transmission at all wavelengths, is preferable. The L , a and b values can be
outlined from the X , Y and Z tristumulus values using the
following equations: L 116Y =Yn 1=3 16; a 500
X =Xn 1=3 Y =Yn 1=3 ; b 200Y =Yn 1=3 Z=Zn 1=3 ,
where Xn 94:825, Yn 100:00 and Zn 107:399 using
the D65 illuminant and 10 observer condition, and X =Xn ,
Y =Yn , Z=Zn > 0:008856. When X =Xn , Y =Yn or Z=Zn are
less than 0.00856, other equations should be used (Hunter
& Harold, 1987). From the L , a and b cartesian coordinates, the polar coordinates may be calculated from:
433
p
b
2
2
C a b and hab arctan
:
a
Table 4
hab , values of 0.05 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and
98 days at 10 C
pH 1.1
pH 3.0
pH 4.1
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
pH 8.0
pH 8.9
pH 9.9
20.8
20.9
20.9
20.9
20.8
20.8
20.6
20.6
20.3
20.2
20.2
20.3
19.7
5.7
5.7
5.7
5.6
5.3
5.2
5.0
5.1
4.8
4.8
4.7
4.5
4.4
)2.5
)2.4
)2.1
)2.2
)2.1
)2.2
)2.2
)0.9
3.4
15.1
52.9
)16.8a
)10.8a
)6.4a
)6.8
)5.2
)4.4
1.4
)21.2a
)24.9a
)2.2
)17.1a
)25.4a
)13.7
)14.8a
)21.7a
)21.0
)8.4
20.8
)13.8a
)18.0a
)25.3
)11.3
25.9
)15.8a
)17.8
)25.7
)16.6
26.2
47.7
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
12.8
12.9
13.1
13.4
12.7
13.0
12.8
12.9
13.0
13.0
13.4
13.2
13.2
)2.8
)2.8
)3.1
)2.8
)4.2
)3.9
)3.8
)3.6
)3.5
)3.1
)2.8
)1.3
)0.2
)6.3b
)5.9
)5.6
)4.5
)8.9
)7.6
)7.5
)6.9
)6.1
)5.6
)5.6
)2.8
)1.6
)1.1b
)26.0b
22.1
)46.8
)28.4
)53.7
)54.9
80.2
)62.6
)67.3
103.6
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
)14.8
)15.1
)15.1
)14.6
)14.3
)14.1
)13.4
)13.1
)12.4
)11.4
)10.5
)8.7
)7.5
)17.4
)17.5
)17.6
)17.4
)17.6
)18.2
)18.2
)18.3
)18.2
)18.1
)18.0
)17.7
)17.9
)25.8a
)25.3a
)25.3
)25.2
)25.2
)25.2
)25.2
)25.3
)25.2
)25.1
)25.2
)25.5
)25.3
)44.3a
)43.9a
)44.9a
)45.5
)45.8
)45.9
)45.8
)46.2
)46.1
)45.9
)46.2
)46.6
)47.5
)49.9a
)50.0a
)50.6
)50.6
)51.1
)51.1
)51.5
)52.4
)52.3
)52.3
)53.3
)54.0
)56.1
)63.3a
)63.5a
)65.2
)65.8
)67.0
)67.3
)70.0
)74.1
)76.5
)78.2
)82.3
)85.5
)89.0
)75.4a
)74.4a
)76.7
)78.2
)80.7
)81.3
)86.2
)92.4
)95.5
)97.5
)101.6
)105.3
)109.2
)88.5a
)83.9a
)87.7
)90.3
)94.5
)95.8
)103.0
)109.8
)112.5
)114.1
)117.8
)122.0
)126.8
)24.2
)24.7
)26.6
)19.0
28.6
48.9
69.6
23.9
24.3
27.5
28.3
33.9
37.5
50.2
59.4
62.2
65.0
68.5
71.6
72.4
27.9
28.4
31.4
32.9
39.4
43.9
63.4
78.8
83.0
85.6
87.5
89.6
17.6
19.4
29.9
39.4
68.3
78.9
88.7
91.0
91.1
92.1
93.9
95.3
96.4
)62.8
)63.3
75.0
80.1
83.7
85.2
89.4
91.8
91.9
92.6
93.5
94.7
94.3
)70.2
)75.0
121.9
)77.8
)81.7
140.6
)40.9
)42.0
28.6
)43.8
)44.8
104.8
99.6
91.0
81.4
80.6
81.2
81.6
82.3
83.1
85.5
86.1
)61.2
111.3
106.1
101.3
95.3
94.3
94.7
95.1
95.4
96.2
97.2
99.3
99.1
)155.5c
107.9
104.8
102.9
99.6
97.5
97.1
96.9
96.8
96.7
96.3
97.2
97.2
)97.7a
)91.8a
)96.9
)100.5
)106.3
)108.1
)115.7
)121.4
)123.7
)125.1
)128.5
)133.1
)138.2
)100.4a
)97.7
)104.2
)108.6
)116.1
)118.4
)125.8
)129.7
)131.9
)133.3
)136.8
)141.5
)147.1
)87.5
)91.8
)98.8
)101.4
)111.4
)114.4
)122.1
)126.9
)129.0
)131.2
)138.8
)152.1
)164.0
)66.5
)72.7
)87.2
)107.5
156.6
145.6
119.2
111.2
108.5
106.4
104.6
103.3
102.5
)70.6
)95.2
113.5
110.7
107.4
106.8
105.3
104.8
104.7
103.8
103.0
102.5
102.4
)155.4
175.5
109.2
105.7
104.5
104.4
103.4
102.6
102.4
101.4
100.5
100.4
100.1
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
pH 10.5
434
with pH, the hues changed with pH along the same lines
for each of the pigments (Fig. 2(a)). The three pigments
had reddish nuances at the lowest pH values. By stepwise
pH increase until 7.3, the colours gradually changed toward more bluish tones. At this pH in freshly made 0.05
mM solutions, 1 showed red-lilac nuance (hab 24),
while 2 and 3 showed blue tones (hab 78 and )101,
respectively). At higher pH-values the hue angles increased again. For each pigment they were nearly similar
in the pH interval 8.0 to 9.9. At pH 10.5, the hue angles
Table 5
hab , values of 0.15 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and
98 days at 10 C
pH 1.1
pH 3.0
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
42.4
42.2
42.2
41.9
41.8
41.8
41.7
41.8
41.8
41.6
41.5
41.2
41.1
25.6
25.8
25.5
25.1
24.0
23.6
22.5
22.1
21.5
21.1
20.1
19.6
17.6
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
38.0
38.1
38.4
38.7
38.8
39.0
39.2
39.3
39.4
39.4
39.7
39.4
39.4
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
)9.7a
)1.1
)0.1
0.3
0.0
0.2
1.2
1.2
2.4
3.9
5.1
7.7
8.6
pH 4.1
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
pH 8.0
pH 8.9
pH 9.9
5.0a
5.1
5.0
4.4
4.3
4.3
3.5
5.5
12.3
24.3
56.9
74.0
78.1
)50.0a
)28.0a
)21.6a
)22.5a
)21.6a
)20.0
)5.1
37.9
57.0
59.8
60.4
62.1
64.0
)47.1a
)51.8a
)27.3
)24.8
)19.5
)14.9
)8.7
1.1
14.3
32.0
33.5
49.5
52.9
)50.7a
)64.1a
)53.3
)44.7
)34.5
)28.9
)10.0
12.0
31.4
46.4
57.3
65.9
69.5
)46.8a
)61.9a
)58.2
)48.2
)33.4
)24.8
10.3
38.2
53.3
59.8
65.9
70.1
71.8
)50.0a
)61.2a
)63.9
)54.3
)33.7
)22.1
25.7
53.2
61.1
64.8
69.1
71.6
72.7
)47.0a
)55.8a
)64.6
)55.6
)33.1
)17.7
39.3
59.0
64.1
66.8
69.8
71.7
72.5
)39.7a
)44.1a
)56.6
)50.2
)23.6
)2.9
50.0
64.2
67.8
69.6
71.5
73.1
73.7
24.1
24.1
25.3
25.5
28.7
31.5
43.6
50.6
53.1
55.4
59.1
62.7
64.7
26.9
27.3
29.5
31.1
38.4
43.9
66.2
76.9
79.6
81.1
83.3
85.8
87.7
23.4
24.5
31.8
40.8
68.6
76.3
82.2
85.2
86.9
88.4
90.7
92.7
94.2
)53.6
)56.5
68.3
76.4
79.3
80.3
83.2
85.3
86.5
87.5
89.3
91.0
92.1
4.4
4.5
4.3
3.7
2.4
2.0
1.9
2.0
2.3
2.4
2.7
3.6
4.8
)8.0b
)7.9
)7.5
)7.3
)8.5
)7.8
)7.8
)7.4
)6.8
)6.5
)6.1
)4.8
)3.9
)13.6b
)10.5
)7.8
)5.9
)9.0
)5.4
)3.3
)0.1
2.6
4.6
7.7
14.3
21.3
)28.9b
)6.5
9.9
)42.3
)40.0
29.6
)46.3
)57.7
49.6
61.0
43.0
60.6
55.6
61.4
65.7
66.9
70.9
75.8
77.7
)51.5
)63.6
94.2
90.9
81.7
84.5
77.5
76.3
76.1
75.6
76.3
77.9
78.2
)56.1
)67.0
146.0
125.3
125.3
109.4
101.7
92.0
86.3
83.9
80.6
78.9
78.3
)59.8
)68.4
170.1
140.2
137.8
124.1
116.5
103.4
96.7
91.3
85.5
81.2
78.9
)34.2
)36.3
)12.5
52.6
60.2
58.0
55.0
52.2
52.2
52.7
53.9
56.5
58.5
)34.8
)36.1
100.6
91.6
80.6
70.4
69.3
70.3
71.2
72.1
73.6
75.4
76.3
)46.9
106.8
101.8
96.9
89.9
83.6
84.2
85.6
86.6
87.4
88.7
90.7
91.7
)171.4c
103.3
99.7
98.9
97.5
95.1
93.6
94.0
94.3
94.3
94.1
93.5
92.5
)5.2a
)4.2
)4.1
)4.1
)4.7
)4.9
)4.9
)5.5
)5.4
)5.2
)5.5
)4.9
)5.2
)22.2a
)19.5a
)18.9
)18.9
)19.3
)19.3
)19.4
)19.5
)19.4
)19.5
)19.5
)19.8
)19.9
)41.2a
)39.2a
)38.2
)38.3
)38.7
)38.8
)39.0
)39.0
)39.1
)39.4
)39.6
)40.2
)40.7
)43.0a
)42.9a
)43.8
)43.9
)44.4
)44.6
)45.5
)46.4
)47.2
)48.2
)50.0
)52.5
)55.0
)58.2a
)55.1a
)55.1a
)55.8
)56.9
)57.1
)59.8
)62.7
)65.0
)67.2
)71.3
)75.7
)79.8
)67.4a
)61.4a
)60.4a
)61.6
)63.1
)63.6
)67.6
)71.7
)75.0
)78.2
)84.0
)90.2
)95.6
)97.4a
)82.0a
)75.4
)77.8
)81.4
)82.7
)88.9
)94.5
)98.7
)103.3
)111.2
)121.7
)130.3
)77.4a
)79.6
)86.3
)91.0
)100.2
)101.8
)113.5
)122.5
)126.6
)130.2
)140.1
)157.6
)172.3
)79.4
)88.6
)104.0
)116.4
)152.8
)169.9
123.5
106.9
103.0
100.9
98.9
97.2
96.3
)73.9
)105.2
116.2
106.1
98.4
97.5
96.2
96.6
97.0
96.9
96.9
96.9
97.4
)153.0
)167.4
102.7
96.7
95.7
95.8
96.0
96.0
96.0
95.6
95.3
94.9
94.7
)72.1a )87.7a
)65.4a )78.0a
)65.8
)70.7
)67.4
)72.8
)69.8
)76.0
)70.5
)76.9
)75.6
)82.8
)80.5
)88.3
)84.4
)92.4
)88.4
)97.0
)95.6 )104.8
)103.9 )114.2
)109.9 )121.2
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
pH 10.5
435
shown by the hue angles (Fig. 2(a)), glucosidic substitution at the aglycone 5 position (pigments 2 and 3)
compared to non-substitution of this position (1), produced a relative large decrease of the hab , values in alkaline solutions. For instance at pH 8.0, in 0.05 mM
solutions, 1 showed a colour between red and orange
(hab 24) and 2 a lilac colour (hab 41), while 3 had
a blue colour (hab 88).
Fig. 2(b) shows visible kmax -values of freshly made
0.05 mM solutions of 13 at the various pH-values.
Table 6
C values of 0.05 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and 98
days at 10 C
pH 1.1
pH 3.0
pH 4.1
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
45.9
45.8
45.7
45.3
45.2
45.2
45.1
45.0
44.9
44.7
44.7
44.4
44.3
40.5
40.5
39.9
39.9
37.8
37.4
36.8
36.6
35.9
35.2
33.4
31.6
28.6
22.1
22.1
21.2
21.9
21.3
21.0
18.8
15.2
10.4
6.4
3.8
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
46.7
46.8
47.0
47.2
47.4
47.4
47.5
47.6
47.7
47.7
47.9
46.6
47.7
23.1
23.0
19.0
18.2
17.1
16.9
17.0
16.6
16.8
16.7
16.0
14.7
14.2
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
69.5
69.3
69.3
69.1
68.9
68.9
69.0
68.8
68.5
68.5
68.2
67.5
67.0
67.9
68.0
68.1
67.8
67.7
66.4
66.4
66.2
65.9
65.6
65.3
64.3
63.8
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
pH 8.0
pH 8.9
pH 9.9
pH 10.5
5.0a
4.3a
4.1a
4.0
4.1
4.0
3.7
3.4
3.7
15.4a
4.3a
2.4
15.2a
9.9a
2.9
13.6a
11.0a
3.5
2.8
2.2
12.2a
10.9a
4.2
3.0
2.2
11.6a
11.0
5.2
3.6
2.4
2.6
11.8
11.4
6.4
4.4
2.7
2.9
3.8
21.5
21.7
19.3
17.7
14.5
13.1
9.5
7.8
7.1
6.7
6.2
5.8
5.0
21.2
21.4
19.8
18.3
14.1
12.0
7.2
5.5
4.8
4.6
4.4
3.9
16.1
16.1
12.8
10.4
7.0
6.6
6.2
5.8
5.4
5.2
4.9
4.5
3.6
28.5
23.8
9.3
10.0
9.2
8.8
7.5
6.7
6.3
5.8
5.4
4.9
4.6
6.3b
6.3
6.1
5.9
6.2
5.9
5.8
5.8
5.7
5.7
5.7
5.4
5.6
1.5b
4.0b
0.8
25.9
1.2
34.7
4.6
0.7
38.3
13.2
0.8
42.2
23.3
1.0
43.2
31.1
1.4
52.8
40.3
1.3
49.1
26.1
6.9
6.9
6.3
5.8
5.5
5.4
5.2
5.2
5.0
4.7
4.7
17.2
11.4
11.4
9.1
7.5
7.1
6.8
6.5
6.2
6.0
5.8
5.4
5.2
14.4c
20.6
16.4
14.0
12.2
11.4
10.4
9.8
9.1
8.6
7.9
6.5
5.7
50.5a
56.8a
59.3
58.8
58.6
58.7
57.9
57.6
56.5
55.4
54.7
52.5
51.9
24.7a
36.7a
41.8a
40.0
39.2
39.2
37.1
35.9
34.2
32.7
31.0
28.5
27.3
38.1a
42.7a
40.5
39.1
37.7
38.4
34.3
31.3
29.1
27.7
24.5
20.9
19.2
29.4a
41.3a
37.8
35.7
32.9
33.1
27.8
23.9
21.9
20.5
18.1
16.0
13.9
28.4a
39.0a
37.0
34.4
31.0
30.8
25.9
22.5
20.8
19.8
17.9
15.8
13.9
31.2a
41.5a
37.6
34.9
31.3
30.8
26.5
23.8
22.5
21.5
19.4
16.7
14.1
34.7a
42.9a
38.9
36.2
32.6
32.1
28.8
26.3
25.0
23.9
21.5
18.1
15.2
41.4a
44.9
40.8
38.5
35.2
34.6
31.8
29.6
27.7
26.3
23.4
19.6
16.1
43.4
43.0
38.7
34.9
29.4
28.1
23.0
20.0
17.4
15.1
11.7
8.4
6.8
35.0
33.2
20.5
10.6
6.9
7.8
10.8
13.9
16.1
17.2
17.9
17.7
16.8
20.2
8.5
31.4
31.8
29.0
28.3
25.5
22.8
21.0
19.6
17.5
15.4
13.4
47.2
37.3
34.5
30.7
26.8
25.7
21.5
18.5
16.9
15.7
14.6
13.1
11.9
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
436
aglycones with two or three hydroxyl groups on the Bring (like cyanidin) achieved the same variation in the
alkaline region as described above, contrary to anthocyanidin 3-monoglucosides with only one hydroxyl
group on the B-ring, which showed almost constant
kmax values for each pigment in this pH region. Thus,
the pattern shown in Fig. 2(b) indicated that more
complex anthocyanins, such as 3 (having two aromatic
acyl groups and 3,5-diglycosidic substitution) may involve the same type of aglycone equilibrium forms at
Table 7
C values of 0.15 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and 98
days at 10 C
pH 1.1
pH 3.0
pH 4.1
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
pH 8.0
pH 8.9
pH 9.9
pH 10.5
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
81.9
81.5
81.4
83.9
83.7
83.6
83.6
83.7
83.3
82.9
82.8
82.1
82.2
70.2
70.4
70.0
72.4
71.0
70.4
69.1
68.7
67.6
66.9
65.5
64.2
60.8
49.8a
50.0
49.0
51.0
50.5
50.3
45.4
35.5
25.4
19.0
15.4
17.6
19.1
22.6a
13.8a
13.0a
13.9a
13.7a
13.3
10.5
10.4
16.2
20.5
24.0
24.8
24.7
32.5a
24.7a
11.7
11.0
9.9
9.0
8.5
7.7
7.4
7.3
7.6
8.8
9.1
27.7a
29.1a
17.7
15.0
12.1
10.8
8.3
7.1
7.3
7.7
8.7
9.8
10.3
22.9a
24.3a
17.5
14.4
10.8
9.5
7.3
7.5
8.6
9.2
10.2
11.1
11.3
22.3a
23.6a
19.4
15.9
10.5
9.0
7.2
8.6
9.8
10.4
11.5
12.3
12.6
21.9a
22.5a
20.4
17.0
10.4
8.5
7.8
9.9
11.2
11.9
12.9
13.7
13.8
24.0a
23.6a
20.6
17.6
9.7
7.9
8.9
11.3
12.7
13.5
14.5
15.3
15.3
47.2
47.6
44.5
42.9
35.4
31.9
24.0
21.2
20.2
19.5
18.6
17.5
16.7
46.9
47.4
45.3
43.6
33.8
28.8
18.4
15.4
14.3
13.8
13.1
12.2
11.3
40.6
40.7
32.3
26.0
18.2
17.4
16.5
15.2
14.1
13.3
12.2
11.1
9.9
49.7
44.4
17.5
25.4
25.4
24.6
21.7
19.5
17.8
16.7
15.3
13.5
12.0
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
78.6
78.6
79.0
79.3
79.6
79.8
80.2
80.4
80.4
80.5
80.7
78.4
80.4
52.9
53.1
52.4
50.9
48.9
50.0
46.6
46.3
46.1
45.8
45.1
41.6
39.9
20.9b
20.8
20.4
20.1
20.1
19.6
19.2
18.9
18.9
18.7
18.8
17.6
17.7
6.1b
5.7
5.2
5.0
5.6
5.0
5.3
5.1
5.1
5.2
5.1
5.2
5.4
13.1b
3.3
3.1
64.7
5.1
2.1
75.7
16.6
1.5
2.0
1.9
2.6
3.0
4.0
5.0
5.8
7.6
10.5
13.7
74.6
39.9
1.1
1.9
1.5
2.7
3.1
4.3
5.6
6.5
8.5
11.6
15.2
73.4
54.5
2.1
2.9
2.8
3.8
4.3
5.7
7.2
8.5
11.1
14.7
18.7
71.5
62.3
3.9
5.0
5.3
6.0
6.6
8.0
9.2
10.9
13.5
17.2
21.4
81.2
75.7
5.2
4.8
6.2
7.0
8.9
10.7
12.4
13.7
15.5
16.8
18.5
77.7
60.2
18.7
21.5
21.4
22.2
21.2
20.3
19.6
19.0
18.1
17.3
17.8
32.5
26.4
33.6
30.8
27.9
24.9
23.2
21.8
20.5
19.4
18.0
16.0
15.9
35.6c
52.9
50.7
48.3
43.2
37.1
33.7
31.9
30.6
29.1
26.6
23.4
23.4
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
79.6a
78.1
77.9
77.9
80.8
80.7
80.8
80.7
80.2
80.2
80.2
80.0
80.2
80.6a
77.6
77.6
77.6
80.6
80.6
80.7
80.9
80.4
80.3
80.5
80.0
80.1
79.0a
77.5a
77.9
77.9
81.0
80.8
81.2
81.3
80.8
80.5
80.4
80.1
80.2
65.4a
71.5a
73.8
73.7
76.4
76.2
75.7
75.5
74.6
73.5
72.4
69.8
68.8
75.8a
72.4a
71.3
71.1
73.5
73.5
71.8
69.8
67.5
65.6
61.6
54.6
49.4
64.4a
66.9a
66.8a
65.9
67.2
67.1
63.5
59.3
55.7
52.8
46.9
39.9
34.8
57.8a
63.8a
64.7a
63.6
64.3
64.0
59.7
55.1
51.1
48.2
42.2
35.8
31.0
59.7a
63.1a
62.5
61.2
61.6
61.1
57.0
52.9
49.7
47.1
42.5
37.3
33.2
48.9a
55.9a
60.1
58.7
59.0
58.4
54.7
51.3
48.7
46.6
42.9
39.2
35.5
46.6a
55.6a
57.7
56.4
56.7
56.0
52.9
50.1
47.8
46.2
43.3
40.1
36.6
56.1a
53.6
51.1
49.3
48.3
47.4
42.8
38.2
34.1
30.5
24.6
18.1
14.9
38.8
40.1
35.2
30.1
19.5
16.6
18.9
28.5
34.1
37.4
40.2
41.4
40.5
24.3
23.6
40.2
47.4
51.7
52.8
53.9
51.4
49.6
47.9
44.5
40.8
37.1
42.3
50.4
55.2
54.2
53.3
52.5
48.3
44.7
42.4
40.5
38.0
35.6
33.4
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
437
Table 8
L values of 0.05 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and 98
days at 10 C
pH 1.1
pH 3.0
pH 4.1
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
pH 8.0
pH 8.9
pH 9.9
pH 10.5
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
81.1
81.1
81.1
81.2
81.2
81.3
81.3
81.4
81.5
81.5
81.6
81.5
81.8
82.3
82.3
82.6
82.6
83.5
83.7
84.0
84.1
84.3
84.5
85.2
85.9
87.2
89.5
89.5
90.0
89.7
90.0
90.1
91.1
92.8
94.6
96.2
97.5
94.9a
96.4a
96.7a
96.7
96.8
96.8
96.9
82.6a
95.2a
97.3
75.8a
85.0a
95.2
75.2a
80.8a
93.5
94.5
95.8
74.3a
77.8a
91.1
93.0
95.1
73.7a
76.0
88.0
91.1
94.4
95.5
72.5
74.0
84.7
88.9
93.6
94.8
96.2
74.8
75.1
78.6
80.7
85.3
87.5
92.8
95.3
96.1
96.4
96.8
97.0
97.8
75.0
75.2
77.8
79.8
85.0
87.8
94.2
97.0
97.9
97.9
98.1
98.7
73.2
73.8
80.3
85.4
93.6
95.7
97.3
97.8
98.1
98.2
98.5
98.6
99.3
62.0
65.9
92.8
94.6
96.0
96.5
97.4
98.0
98.0
98.3
98.6
98.7
98.8
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
81.5
81.5
81.4
81.4
81.6
81.6
81.6
81.4
81.5
81.5
81.4
78.9
81.3
90.5
90.6
92.1
92.4
93.2
93.2
93.1
93.1
93.3
93.2
93.5
90.6
93.6
96.5b
96.6
96.7
96.9
96.9
96.8
96.2
97.1
97.0
97.1
97.1
94.0
96.7
98.2b
96.6b
98.6
80.7
97.6
73.2
94.7
98.2
69.3
87.9
98.0
65.4
79.8
97.7
64.4
73.9
97.2
67.1
74.2
96.5
67.3
79.6
97.1
97.5
97.7
97.4
97.6
97.8
98.0
98.1
98.2
95.5
98.5
80.6
96.3
97.9
97.8
98.1
98.1
98.2
98.4
98.5
98.6
98.7
96.0
98.9
83.3c
96.9
97.5
97.5
97.8
97.6
97.8
97.9
98.0
98.1
98.2
95.6
98.8
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
66.0
66.0
66.2
66.2
66.3
66.3
66.6
66.7
66.9
67.1
67.7
68.0
68.8
66.5
66.5
66.6
66.6
66.6
67.2
67.6
67.6
67.6
67.8
68.1
68.2
68.7
72.5a
68.0a
67.9
68.1
68.3
68.2
69.0
69.3
69.5
69.9
70.6
71.4
71.5
82.7a
74.3a
70.4a
71.3
71.6
71.6
73.2
73.8
74.5
75.3
76.2
77.2
77.7
72.1a
68.5a
70.1
71.0
72.0
71.5
74.4
76.2
77.1
77.7
79.8
81.2
82.4
76.0a
65.5a
68.0
69.4
71.3
71.1
74.8
77.2
78.1
78.8
80.3
80.8
81.7
75.3a
65.5a
66.7
68.7
71.0
71.1
74.9
77.2
78.1
78.6
79.9
80.7
81.5
72.2a
62.1a
65.6
67.7
70.6
70.9
74.6
76.8
77.6
78.0
79.6
80.7
82.6
69.3a
60.8a
64.7
67.1
70.3
70.8
74.0
76.3
77.0
77.6
79.4
81.0
83.0
63.2a
59.4
64.0
66.3
69.8
70.5
73.6
75.5
76.3
77.3
79.3
81.2
83.3
57.8
58.8
62.9
65.7
71.1
72.5
77.3
79.8
81.4
82.9
85.5
87.5
89.4
56.3
57.3
65.8
73.6
83.8
85.4
89.2
91.9
93.5
94.4
95.6
96.1
96.8
55.3
64.1
93.2
94.7
95.7
96.0
97.0
97.2
97.2
97.3
97.5
97.5
98.2
57.2
72.5
95.3
96.2
96.6
96.7
97.2
97.3
97.3
97.4
97.4
97.6
97.9
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
438
hamnosyl)glucoside-5-glucoside, petanin, were compared with similar values of the six common anthocyanidin 3-glucosides (Cabrita et al., 2000; Fossen, Cabrita,
& Andersen, 1998), it was noticed that petanin in contrast
to anthocyanin 3-monoglucosides, showed relatively high
e values in slightly alkaline solutions. This hyperchromic
eect in slightly alkaline solutions should thus be attributed to 3,5-diglycosidic substitution and not aromatic
acylation of the anthocyanin.
Table 9
L values of 0.15 mM cyanidin 3-glucoside (1), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) and cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) at pH-values from 1.1 to 10.5 measured initially (0), after 1 hour (1 h), 1 day (1 d), 2, 5, 7, 14, 21, 28, 35, 49, 70 and 98
days at 10 C
pH 1.1
pH 3.0
pH 4.1
pH 5.1
pH 6.0
pH 6.6
pH 6.8
pH 6.9
pH 7.2
pH 7.3
pH 8.0
pH 8.9
pH 9.9
pH 10.5
(1)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
63.7
63.4
63.6
66.3
66.3
66.3
66.5
66.7
66.8
66.9
67.0
66.6
67.2
63.0
63.1
63.3
66.1
66.6
66.9
67.5
67.7
68.1
68.2
68.9
69.5
71.1
69.6a
69.9
70.6
73.6
73.9
74.0
76.6
81.2
85.5
88.6
91.3
92.3
92.7
65.5a
80.7a
82.6a
86.4a
86.3a
86.7
87.7
88.2
86.6
86.3
85.6
84.5
86.3
39.9a
60.7a
81.7
87.0
87.9
88.7
88.4
88.6
88.5
90.4
88.0
87.9
87.7
33.5a
41.4a
67.6
76.4
79.6
80.6
82.9
84.7
85.2
87.1
87.5
88.5
89.5
35.3a
40.5a
63.7
73.8
78.2
79.8
83.5
86.1
87.2
88.3
89.0
89.4
90.4
33.3a
37.1a
56.5
67.6
75.2
77.7
83.4
86.6
87.1
87.9
88.6
89.2
90.1
32.2a
35.0a
51.3
62.8
73.3
76.8
83.7
86.5
87.0
87.5
88.3
88.9
89.9
31.1a
33.7a
48.2
58.9
71.4
75.6
82.5
85.2
85.9
86.3
87.3
88.2
89.1
38.7
39.4
44.7
51.4
61.4
66.2
77.8
82.4
84.1
85.2
87.0
88.8
90.1
38.7
39.1
43.8
51.1
64.7
71.5
87.5
92.4
93.7
94.2
94.6
95.5
96.2
39.3
40.3
53.9
68.6
86.6
90.2
92.7
94.0
94.5
95.2
95.9
96.6
97.3
24.3
28.2
75.4
85.9
89.1
90.1
92.3
93.5
94.2
94.7
95.2
96.2
97.0
(2)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
69.5
69.6
69.4
69.4
69.6
69.6
69.4
69.4
69.2
69.4
69.4
67.2
69.4
76.9
77.1
77.5
78.2
79.2
80.0
80.0
80.4
79.9
80.5
80.6
78.6
82.1
89.4b
89.6
89.9
90.1
90.3
89.8
90.3
90.7
90.7
90.7
90.8
87.8
90.6
94.5b
95.0
95.3
95.4
95.4
95.2
95.4
95.2
95.1
94.9
95.0
91.8
94.6
89.2b
92.7
95.9
49.9
89.5
95.3
36.9
79.7
94.6
94.6
94.2
94.7
94.2
94.3
94.2
93.7
93.4
89.9
91.9
31.3
60.8
93.5
93.6
93.4
94.1
93.3
93.4
93.4
92.8
92.4
88.8
90.5
29.1
47.2
92.0
92.4
92.2
92.8
92.2
92.3
92.2
91.4
90.9
87.1
88.6
27.6
38.0
89.6
90.7
90.7
91.4
90.5
90.9
90.3
90.0
89.5
85.8
87.3
35.6
43.1
88.1
91.1
91.3
91.8
91.3
90.6
90.2
90.1
90.0
87.2
89.8
35.1
47.3
87.4
90.7
89.9
89.0
90.1
91.2
92.0
92.4
93.1
90.7
93.5
52.3
84.8
90.2
92.4
92.2
91.9
92.8
93.6
94.2
94.7
95.2
93.0
96.1
55.5c
87.7
90.4
93.3
93.5
93.1
93.1
93.5
93.9
94.1
94.3
91.6
94.3
(3)
0
1h
1d
2d
5d
7d
14 d
21 d
28 d
35 d
49 d
70 d
98 d
56.7a
46.0
46.1
46.2
48.5
48.5
48.9
49.0
49.2
49.8
50.2
50.8
51.6
48.1a
45.1
45.1
45.1
47.3
47.3
47.5
47.4
47.5
47.6
47.8
47.9
48.1
50.3a
40.8a
39.9
39.9
42.1
42.3
42.6
42.7
42.9
43.3
43.6
44.2
44.5
52.5a
40.7a
36.4
36.5
39.0
39.2
40.0
40.0
40.6
41.7
42.4
44.2
44.7
35.4a
33.7a
35.4
35.6
38.2
38.1
39.7
41.1
42.0
42.7
44.8
48.6
50.8
42.3a
33.3a
31.6a
32.3
35.1
34.9
37.5
40.0
41.6
42.7
46.2
50.6
53.2
46.6a
33.8a
30.4a
31.4
34.4
34.3
37.3
40.3
41.9
43.7
47.3
52.0
53.3
41.8a
30.9a
29.4
30.7
34.0
34.0
36.9
39.9
41.7
43.0
46.5
49.8
52.3
53.6a
39.5a
29.6
30.8
34.3
34.4
37.2
40.1
41.6
42.9
45.9
49.1
51.8
57.3a
38.4a
29.8
30.9
34.5
34.8
37.5
40.3
41.6
42.9
45.8
49.0
52.2
28.2a
27.8
30.6
32.5
38.8
39.7
46.2
52.0
55.2
58.0
63.4
69.2
72.7
22.7
24.2
29.1
35.2
53.3
57.4
69.9
77.6
81.5
83.9
87.0
88.4
89.5
19.6
23.5
73.8
80.2
86.3
87.0
89.9
91.1
91.4
91.8
92.4
92.4
93.6
27.6
35.8
82.5
85.3
90.4
90.8
91.7
91.9
92.1
92.3
92.8
92.7
93.4
When the L -value became higher than 95, and the C -value lower than 5, no more measurements were recorded.
Some undissolved pigment was still present.
b
The colour turned lighter during the preparation time.
c
The colour turned more green (less blue) during the preparation time.
a
(b)
60
40
hab
(a) 25
20
15
10
5
0
-5 0
-10
-15
-20
439
20
20
40
60
80
100
20
-20 0
20
-20
40
60
80
100
-40
(c) 120
(d)
130
70
hab
80
20
30
-30 0
20
40
60
-80
80
100
40
60
80
100
-70
-120
-130
days
days
Fig. 5. hab values variations with time (days) for 0.05 mM cyanidin 3-glucoside (1) (s), cyanidin 3-(200 -glucosylglucoside)-5-glucoside (2) (M) and
cyanidin 3-(200 -(2000 -sinapoylglucosyl)-600 -sinapoylglucoside)-5-glucoside (3) () at pH 1.1 (a), pH 4.1 (b), pH 6.9 (c) and pH 8.9 (d).
440
Acknowledgements
The authors thank Polyphenols Laboratories AS for
instrumental support. K.T. acknowledges The Norwegian Research Council for a fellowship.
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