A Research Note

Maillard Browning Reaction of Sugar-Glycine Model Systems:

Changes in Sugar Concentration, Color and Appearance
FELIX

G. R. REYES,

BOONTHONG

POOCHAROEN,

ABSTRACT
The reactivities of glucose, fructose, and sucrose with glycine (1:l
molar ratio) at 60C and pH 3.5, were compared over 280 hr. While
fructose initially browned at a faster rate, it was overtaken by glucose after 80 hr. Initially more fructose than glucose was consumed, but the reverse was true after 60 hr. Sucrose was readily
hydrolyzed under these reaction conditions and underwent MailIard
browning reactions, its color and appearance being similar to the
glucose solutions at the later stages of the experiment. Glucose and
sucrose solutions developed considerable haze while the fructose
glycine solution remained clear.

INTRODUCTION
BROWNING REACTIONS in foods continue

MAILLARD
to be an active area of research because of their important

roles in color, flavor and nutritional

quality. In addition,
some of the products produced from these reactions may
have toxicological
significance (Adrian,
1974; Tanaka et
al., 1977). The availability of crystalline fructose and corn
syrups with varying proportions
of glucose and fructose
offers a wide range of sugars which are available for product
formulation.
Thus there is practical interest in the compara-

tive reactivity of these sugars and their influence on quality.

Previous workers (Bobbio et al., 1973; Shallenberger and
Birch, 1975) have reported that fructose initially browns at
a faster rate than glucose but is later overtaken by glucose.
It was the purpose of this investigation to compare the
reactivity of glucose, fructose, and sucrose with glycine
under accelerated

storage conditions

over an extended reac-

tion period. In addition to measuring the absorbance at

420 nm, the change in glucose and fructose

concentration

was determined as well as Hunter color and appearance

parameters.
MATERIALS & METHODS
Sample preparation
Model systems consisted of 1 .OM solutions of sugar (D-fructose,
D-glucose or sucrose) and l.OM glycine at pH 3.5. Controls containing only the sugar were used to determine the contribution to color
formation by caramelization. The pH of all the solutions was adjusted with O.lN HCl or O.lN NaOH. Eight ml portions of the solutions were distributed in 10.0 ml screw-cap tubes, sealed fingertight,
and held in a water bath at 6O.OC. Tubes were periodically removed for analyses during the experiment. Color and pH were
monitored during storage; no change in pH was observed.
Spectrophotometric measurements
The absorbance at 420 nm was determined on a Beckman
ACTA CIII spectrophotometer. Dilutions were made with distilled
water, the maximum dilution for any determinations being 1: 100.

1376-JOURNAL

OF FOOD SCIENCE-Volume

47 (19821

E. WROLSTAD

Hunter color measurements

Hunter L, a, b values were measured in the transmission mode
using a Hunter Model D 25 P-2 Color Difference Meter. Samples
were diluted 1:50 and read in cells with a 0.5 cm pathlength. Measurements were made with the specular component both included
and excluded to allow calculation of percent haze. The ScofieldHunter Index AE = (Ll - Lz)* + (al - a$* + (bl - b2)* where
Lr , al and bl represent the color at time t and L2,a~ and b2 repre-

sent initial color, was calculated as was the saturation index,

(a* + b*).

Glucose and fructose determinations

Glucose and fructose content were determined enzymically

usingthe glucose/fructosekits from BoehrlngerMannheimBiochemicals (Indianapolis, IN), accordingto the manufacturersinstructions.

After appropriate dilutions, aliquots were combined with reagents
and the absorbancedeterminedat 340 nm.
RESULTS & DISCUSSION
TABLE 1 shows the change in absorbance at 420 nm for
glucose-, fructose-, and sucrose-glycine solutions over 280 hr.
While the fructose-glycine solution initially browns at a
faster rate, it is overtaken by both glucose- and sucroseglycine solutions after approximately 80 hr. Other workers
(Bobbio et al., 1973; McWeeny, 1973; Hodge and Osman,
1976) have reported similar results in comparing glucoseand fructose-amino compound solutions. There was no
increase of absorbance in the model system solutions containing only the sugar, indicating that there was no contribution to color formation due to caramelization. Fig. 1
compares the loss of glucose and fructose in the glucoseand fructose-glycine solutions. Fructose concentration
decreases faster than glucose initially, but the loss of
glucose overtakes fructose after 60 hr. These changes are
consistent with the browning rates observed in Table 1.
Thus the differences in browning are not due to the chromophoric attributes of the pigment formed. Glucose and fruo
tose concentrations were measured in the sucrose-glycine
solution and a similar pattern followed in that fructose
concentration surpassed the glucose concentration after
80 hr. Under different reaction conditions, Burton et al.
(1963) and Newell et al. (1967) reported higher initial reactivity for fructose as compared to glucose. Wolfrom et al.
(1974) studied the behavior of fructose, glucose, and
sucrose with glycine at a 5:l molar ratio at 65C and a
pH of 6.1 for 10 hr. The amount of.browning in the glucose
solution caught up with the fructose solution within 10
hr. There was negligible browning in the sucrose-glycine
solutions under their experimental conditions. We measured over 50% sucrose hydrolysis after 40 hr at pH 3.5 and
60C and our results show that sucrose initially browns at
rates similar to glucose- and then surpasses the glucoseglycine system (Table 1). The sucrose system has a potential
reducing

The authors are affiliated

with rhe Dept. of Food Science & Technology,
Oregon State Univ., Corvallis,
OR 97331. Author
Reyes is
on sabbatical
leave from
Universidade
Estadual
De Campinas/
F.E.A.A.
- Campinas S.P. - Brasil 13100. Reprint
requests should
be addressed to Dr. Wrolstad.

and RONALD

sugar concentration

twice that of the monosac-

charide systems and accounts for that systems greater

degree of browning during the later stages of experiment.
The absorbance readings (Table 1) and visual appearance of
the samples were confirmed by Hunter color measurements.
The Hunter L values were much higher for the fructoseglycine solution

than the glucose- and sucrose-glycine

solu-

Table l-Change

in absorbance

and Hunter

color

measurements

Fructose
Hunter

solutions

during

storage at 60.0C

measurements

Hunter

Absorbance
(420nm)

L1

AE2

613

Haze
(%I

0
3
6
9
12
24
48
72
96
123
164
188
212
236
260
284

0.00
0.03
0.09
0.16
0.25
0.83
2.92
5.58
10.4
16.1
25.0
30.3
34.0
36.2
45.5
50.0

96.1
96.1
96.1
96.1
96.1
96.0
95.6
95.2
94.2
93.2
92.1
90.1
89.4
89.0
86.9
66.2

0
0
0
0.1
0.22
0.73
2.83
5.03
a.70
12.8
15.8
21.0
22.8
23.8
27.5
29.2

0.41
0.51
0.54
0.61
0.73
1.24
3.30
5.46
9.00
12.96
15.75
20.63
22.32
23.21
26.44
28.01

1.8
1.9
1.8
1.9
1.9
1.8
2.0
1.9
1.9
2.0
2.0
2.2
2.2
2.3
2.3
2.3

Absorbance
(420nm)
0.00
0.01
0.02
0.03
0.05
0.24
1.50
4.39
11.6
24.7
49.0
63.6
79.7
107
112
121

and pH 3.5

Sucrose

Glucose

Time
(hrs)

1 L = Hunter L value
2 AE = Scofield-Hunter
3 SI = Saturation
Index

of sugar-glycine

Hunter

measurements

L1

AE2

S13

96.3
96.3
96.3
96.3
96.3
96.2
95.7
94.6
91.9
87.6
63.6
74.6
70.4
64.2
-

0
0
0
0
0.10
0.42
2.83
7.95
18.1
29.9
36.7
46.1
48.9
52.3
-

0.57
0.57
0.57
0.57
0.64
0.94
3.26
8.25
18.0
29.0
34.9
41.0
41.8
41.5
-

Haze
(%I
2.3
2.3
2.2
2.2
2.2
2.2
2.2
2.2
2.3
2.3
2.4
3.3
11.4
45.6
46.1
42.9

Absorbance
(420nm)
0.00
0.01
0.01
0.02
0.04
0.21
1.63
4.75
16.3
38.2
78.0
108
139
195
216
244

measurements

L1

AE2

S13

95.9
95.9
95.9
95.9
95.9
95.9
95.7
95.1
93.1
89.1
85.7
77.4
72.6
66.2
63.4
59.6

0
0
0
0
0
0.14
1.47
4.49
13.2
24.8
31.7
41.8
39.6
49.4
51.0
53.2

0.71
0.71
0.71
0.71
0.71
0.82
2.16
5.12
13.6
24.6
30.7
38.1
39.6
40.1
39.9
39.6

Haze
(o/o)
2.2
2.1
2.1
2.2
2.2
2.1
2.1
2.1
2.1
2.1
2.2
11.0
la.7
36.6
43.3
55.2

Index

tions during the later stages of the experiment. Fructose

showed a much lower change in both the Scofield-Hunter
Index (AE) and the saturation index (SI) than the glucoseand sucrose-glycine solutions (Table 1). The glucose and
sucrose samples developed considerable haze in the later
stages of the experiment (over 40% haze after 240 hr)
whereas the frucose solution remained clear (Table 1). This
important appearancequality factor suggeststhat the degree
of polymerization of glucose-derived melanoidins was much
greater than fructose-derived melanoidins under these experimental conditions.
These results show that gJucoseundergoes more browning than fructose during prolonged reaction times under
these experimental conditions. They illustrate that initial
reaction rates may not be predictive of eventual product
formation. These findings point out another factor for consideration when selecting sweeteners for food products
where quality deterioration due to browning reactions
during storage may be a significant problem.
REFERENCES
Adrian, J. 1974. Nutritional
and physiological
consequences of the
Maiilard reaction. World Rev. Nutr. Diet. 19: 71.
Bobble,
P.A., Bobbie,
F.O., and Trevisan, L.M.V.
1978. Estudos
sobre a reacao de MaiBard. 1-Efeitos
da temperatura
e do pH.
An. Acad. Bras& Cienc. 46: 419.
Burton,
H.S.. McWeeny,
D.J.. and Bfltchffe.
D.O. 1963. Nonenrymic browning.
Development
of chromophores
in the glucoseglyeine and sucrose-glycine
systems. J. Food Sci. 28: 631.
Hodge, J.R. and Osman, E.M. 1976. Carbohydrates.
In Food
Chemistry,
Ed. O.R. Fennema, p. 86. Marcel Dekker, Inc., N.Y.
McWeeny.
D.J. 1973. The role of carbohydrate
in nonenrymic
browning.
In Molecular
Structure
and Function
of Food Carbohydrate.
Ed. Birch, G.G. and Green, L.F., p. 26. John Wiley &
Sons. New York.
Newell, J.A.. Mason, M.E.. and Matlock,
R.S. 1967. Precursors of
typIcal
and atypical
roasted peanut flavor. J. Agr. Food Chem.
16(6): 767.
ShaBenberger.
R.S. and Birch, G.G. 1976. Sugar Chemistry,
p.
189. AVI Pubhshing Co., Inc., Westport, CT.
Tanaka, M., Rimiagar,
M., Lee, T-C., and Chickester,
C.O. 1977.
Effect
of MaiIlard
browning
reaction
on nutritional
quality
of
protein.
In:
Protein
Crotalhking-Nutritional
and
Medicl
Consequences.
Ed. M. Friedman,
p. 321. Adv. Exp. Med. Biol.
86B. Plenum Press, New York.

3ol------

40

80

120
160
Time (hr)

200

Fig. 1 -Consumption
of glucose and fructose in the glucosefructose-glycine
systems during
storage at 6O.OC and pH
I% consumption
represents the % individual
sugar lost).

1
240

and
3.6.

Wolfrom,
M.L., Kashimura,
N., and Horton,
D. 1974. Factors affecting the Mailiard browning
reaction between sugars and amino
acids. Studies on the nonenzymic
browning
of dehydrated
orange
juice. J. Agr. Food Chem. 22: 796.
MS received 6/27/81: revised l/26/82;
accepted l/26/82.
The senior author
expresses his appreciation
to Fundacao
de
Amparo a Pequisa do Estado de Sao PauIo, Brasii for a post-doctoral
study grant.
This work was supported in part by grant no. 107090064
from the
Pacific Northwest
Regional Commission.
Technical
Paper No. 6900 from the Oregon Agricultural
Experiment Station.

Volume 47 (1982)-JOURNAL

OF FOOD SCIENCE-

1377