Journal of Food Engineering 109 (2012) 561–570

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Influence of drying and hydrothermal treatment of corn on the denaturation

of salt-soluble proteins and color parameters
Sylvanus Odjo a, Paul Malumba a,b,⇑, Joseph Dossou c, Sebastien Janas a, François Béra a
a
University of Liege, Gembloux Agro-Bio Tech, Food Engineering Laboratory, Passage des Déportés, 2, B-5030 Gembloux, Belgium
b
University of Kinshasa, Agricultural Faculty, BP 14071 Kinshasa 1, Congo
c
University of Abomey Calavi, Department of Nutrition and Food Sciences, 01 P.O. Box 526 Cotonou, Benin

a r t i c l e i n f o a b s t r a c t

Article history: The effect of heat treatments (drying and hydrothermal treatment) on the extractability of salt-soluble
Received 26 August 2011 protein (SSP) was assessed using Promatest methodology for corn kernels heated between 60 °C and
Received in revised form 19 October 2011 120 °C. During drying, the evolution of the grain moisture content is fitted using the analytical solution
Accepted 20 October 2011
of Fick equation developed by Crank (1979) for spherical material. The decrease of extractible salt-soluble
Available online 30 October 2011
protein during heating is forecasted using a first and a second order ordinary differential equation. It was
found that temperature; moisture content and time of processing greatly influence the kinetic denatur-
Keywords:
ation of SSP of corn kernels. The evolution of extractible SSP content of corn kernels during drying at high
Corn
Drying
temperature is more correctly described with second order kinetic than with the first order kinetic reac-
Proteins tion. The Hunterlab color parameters of corn also vary during drying. Lightness and color intensity
Colors parameters decrease while yellowness, redness, chroma and hue angle increase through drying time. Most of these
Heat treatment Hunterlab color parameters are highly correlated with the salt-soluble proteins content and therefore
could be used as indicators of excessive heat treatment and denaturation of salt-soluble proteins in corn
kernels.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction trial processes, modifying the quality of products and by-products

Corn (Zea mays L.) is the most abundant cereal grain produced
in the world and is a staple food for large groups of people in Latin
America, North America, Asia, and Africa (Serna-Saldivar, 2004). It
provides around 42 million tons (Mt) of protein a year, which rep-
resents approximately 15% of the world annual production of food
crop protein (Li and Vasal, 2004).
To improve the efficiency of post-harvest manufacturing of
corn, industry spended considerable resources on improvement
of process control, on more efficient equipment and on the devel-
opment of corn hybrid that decrease the variability and reduces
production costs (Ramírez et al., 2008). However, a great variability
is still observed according to the thermal history of grain. Studies
performed the last 60 years showed that drying temperature and
initial moisture content of kernel affect significantly the products
quality submitted to the wet-milling process. Although high drying
temperatures reduce drying time and allow high flow production
during harvesting periods, they may affect the physicochemical
properties and the performance of unit operations of several indus-
⇑ Corresponding author. Address: University of Liege, Gembloux Agro-Bio Tech,
Food Engineering Laboratory, Passage des Déportés, 2, B-5030 Gembloux, Belgium.
Tel.: +32 81622263; fax: +32 81601767.
E-mail address: paul_malu@yahoo.fr (P. Malumba).
recovered (Malumba et al., 2011). Even if it is advised to dry corn at
low temperatures, it is nowadays common to find industrial dryers
and pilot plant-size bed dryers operating with air heated above
120 °C (Pallai et al., 1987) in spite of consequences of these tem-
peratures on properties of corn and its derivatives (Malumba
et al., 2008).
During high temperature drying, corn grains undergo alterations
such as stress crack (Gustafson et al., 1979), protein denaturation
(Lupano and Anon, 1987; Courtois, 1991; Mourad et al., 1996;
Malumba et al., 2008), change in functional properties of starch
recovered and loss of corn kernel millability (Lasseran, 1973;
Malumba et al., 2009a,b). In the post-harvest manufacturing of
corn, drying temperature and initial moisture content of kernel af-
fect significantly the products quality submitted to the wet-
milling process (Jayas and White, 2003; Eckhoff and Watson, 2009).
Many studies were performed in order to find a repeatable and
rapid test that allow to detect excessive heat treatment of grains,
related to the lost of processes performance and quality of manu-
factured products in the cereal industry (Linko, 1961; Holaday,
1964; Heusdens and Macmasters, 1967; Brown et al., 1979;
Eckhoff and Watson, 2009; Weller et al., 1988; Wehling et al.,
1993; Rausch et al., 1997; Lasseran, 1973; Wight, 1981; Malumba
et al., 2009a). For the wet-milling industry, damages caused by the
high temperature drying are still difficult to detect. Methods

0260-8774/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.10.023
562 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570

Nomenclature

L⁄ lightness P extractible salt-soluble protein content (equivalent mg

a⁄ redness BSA)
b⁄ yellowness k reaction rate (s1)
DE color intensity D decimal reduction time (s1)
DC chroma (DE) z temperature increase require to reduce the decimal
H hue angle reduction time by a factor of 10 (°C)
Deff effective moisture diffusivity in corn (m2 s1)
X corn kernel moisture content (kg water/kg dry matter) Subscripts
M total amount of diffusing water entering or leaving the 0 at the initial time
corn kernel 1 first order
Ea activation energy (kJ mol1) 2 second order
d grain diameter (m) e experimental value
t processing time (s) p predicted value
N number of terms in the numerical series ref reference value
EBSA equivalent mg bovine serum albumin t value at a t time
SSP salt-soluble protein 1 value at infinity
RMSE root mean square error

developed to detect these damages are either laborious, time con-

2. Materials and methods
suming or difficult to implement in practice. Recently a standard
operating procedure was published that established the Promatest
2.1. Fluidized-bed drying of corn kernel
(measurement of extractible SSP – salt-soluble protein) as a refer-
ence method for the assessment of the thermal shock suffered by
The corn kernel used for this study was a flint corn of Baltimore
cereal after their harvesting. In order to link the loss of SSP solubil-
variety. Samples were received in the laboratory immediately after
ity with the kinetic of drying, it is necessary to assess the relation-
harvesting and stored at 20 °C in sealed plastic bag until drying.
ship between temperature, drying rate, SSP denaturation and other
Before each drying, one sealed plastic bag of corn was equilibrated
physicochemical properties of grains during the drying.
at laboratory temperature for one night. The moisture content of
Until now, very few studies were focused on the kinetics of corn
corn after opening of the bag was about 38% w.b.
protein denaturation. Janas et al. (2010a) and Mourad et al. (1996)
Drying was performed in the laboratory fluidized-bed dryer
studied the kinetics of SSP denaturation during corn drying as a
used by Janas et al. (2010a). During the drying process, the air tem-
function of moisture content and temperature. Courtois (1991)
peratures were measured with type TTT-T-30-SLE thermocouples
pointed out that the solubility of corn SSPs follows a second order
from OMEGA (England), air relative humidity with probes TR200
kinetic. Following the SSP content of grains during their fluidized-
from NOVASINA (Switzerland) and air velocity with a TEST0 445
bed drying between 50 °C and 100 °C, Janas et al. (2010a) described
(Germany) anemometer. Thermocouples and air humidity probe
the evolution of SSP of grain with a first order kinetic model with a
signals were measured with a 3595551H UNIVERSAL IMP from
reaction rate depending on the instantaneous moisture content of
SOLARTRON (England), and recorded with a program written in
grain. Mourad et al. (1996) proposed to forecast experimental data
LABVIEW 5.1. Air velocity data were recorded with the TESTO LOG-
of SSP denaturation from a flotation fluidized drying bed, per-
ICIEL-COMFORT ‘‘Light’’ interface. The accuracy of temperature,
formed between 50 °C and 120 °C, with a second-order kinetic con-
humidity and velocity measures were respectively of 0.1 °C, 0.1%
taining a moisture content depending parameter. Neither Janas
and 0.2 m s1. The drying air was taken from the environment at
et al. (2010a) nor Mourad et al. (1996) compared the models they
25 ± 1 °C was heated on the onset temperature.
proposed with other kinetic models in order to understand mech-
Experiments were carried out at 60, 80, 100 and 120 °C. During
anism that lead to the denaturation of SSP during drying. Both
processing, corn samples of approximately 100 g were periodically
Mourad et al. (1996) and Janas et al. (2010a) pointed out that mois-
collected through drying time. About 20 g were used to determine
ture content of grain has a great influence on the SSP denaturation
the moisture content and the remain was equilibrated at room
kinetics during high temperature drying. Unfortunately, during
temperature and conserved in sealed pots at 10 °C for further
drying, local moisture content of grain change simultaneously with
analyses.
the temperature, particularly at the beginning of drying, so that the
For each drying temperature, three trials were performed at dif-
effect of moisture content in the denaturation rate of SSP is not
ferent days. During these dryings, air velocity and relative humid-
known with precision.
ity were measured downstream of the drying chamber and were
The aim of the present study was to:
respectively in the range 5 ± 0.2 m s1 and 40 ± 5%. Considering
the drop of pressure gradient in the drying chamber, air velocity
 Study the effect of temperature on the drying rate of corn ker-
was keep constant by adjusting power supplied to the vacuums
nels and on the denaturation of their SSPs.
of dryer.
 Compare first-order and second order kinetics models as mean
to forecast the denaturation of salt-soluble during corn drying
and heat-moisture treatment of corn flour maintained at con- 2.2. Determination of moisture content of corn kernel
stant moisture content.
 Assess relationship between SSP denaturation and change in the The moisture content of corn kernels and flour was determined
color parameters of corn flour as observed during the corn dry- in triplicate on ±5 g by differential weighing after oven drying at
ing process. 105 ± 2 °C during 48 h.
 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570
2.3. Mathematical modeling of water desorption during drying
In order to estimate the influence of temperature on the drying
rate and to forecast the drying kinetic, a simple mass transfer mod-
el was used. According with Prachayawarakorn et al. (2004) corn
kernels were assumed to be homogen. It was also assumed that
their volume does not change during drying and tempering so that
Ficks second law of diffusion could be applied to describe the mois-
ture transfer inside grain:
@X
¼ r  ðDeff rXÞ
@t
where X represents the corn kernel moisture content (d.b.) and Deff,
the effective moisture diffusivity.
Considering the supposed spherical geometry of corn kernels,
the total amount of diffusing water entering or leaving the corn
kernel was calculated using the analytical solution developed by
Crank (1979):
! SSP from flours obtained after the milling of corn kernels dried
Mt 6 X
1
1 Deff N2 p2 t
¼1 2 exp
M1 p n¼1 n2 d
2 100 ml of buffer prepared with 6.8 g of monopotassium phosphate
where Mt represents the total amount of diffusing water leaving the
grain at a t time and M1, the one at infinity. Then the moisture con-
tent of corn kernel at any time can be determine by Eq. (3):
" !#
6 X 1
1 Deff N2 p2 t
Xt ¼ X1  ðX 1  X 0 Þ exp 
p 2
n¼1
n2 d
2
The equivalent radius of grains was determined using the vol-
ume of whole corn kernel with the magnetic resonance imaging
(MRI) technique as described by Janas et al. (2010a). The average
volumes of the corn kernel used in this study was 1.80  107 m3.
Effective moisture diffusivities were obtained by minimizing
the Root Mean Square (RMS) between experimental and predicted
values:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P Serum Albumin (EBSA).
ðX e  X p Þ2
RMS ¼
n massie brilliant blue G250 from Merck (Germany) in 1000 ml of
Prachayawarakorn et al. (2004) stated that the moisture diffu-
sion inside of corn kernels depends strongly on the temperature
and frequently also on the moisture content. The dependence of
effective diffusivity on temperature was modelled by an equation
of Arrhenius.
Ea
D ¼ D0 eRðTþ273Þ
where Deff (m2 s1) represents the moisture diffusivity, Ea the acti-
vation energy according to the Arrhenius theory, R (kJ kmol1 K1)
is the universal gas constant.
2.4. Hydrothermal treatment of corn flour at constant moisture
content
In order to assess the effect of moisture content on the denatur-
ation of corn protein, corn flour prepared at fixed moisture content,
were submitted to isothermal treatment at temperature between
60 °C and 120 °C. For this purpose, unheated corn kernels were first
freeze-dried using a HETO DRYWINNER (model DW8, Denmark)
and milled using a laboratory grinder IKA M20 (Germany). The
moisture levels of cornflour samples were adjusted at 4%; 17%;
25%; 33% and 61% (d.b.) by adding the appropriate amount of dis-
tilled water to the lyophilized cornflour and equilibrated for 24 h at
4 °C. Approximately 35 g of mixture were well stirred and sealed in
563
cylindrical stainless steel tubes (Length: 100 mm, thickness: 2 mm,
and extern diameter: 30 mm). The hydrothermal treatment
procedure was performed by immerging the cylindrical stain-
less steel tube in a HAAKE N2 oil bath at 60 °C, 80 °C, 100 °C and
120 °C.
The temperature of the oil bath, on the surface and within the
tube was measured using thermocouples type T from OMEGA
(England), whose signals were measured with an Ellab TM 9608
digital interface. In all cases, the onset temperature was reached
rapidly. Heat treated tubes were collected after 30 min, 1 h, 2 h;
3 h, 6 h and 10 h and immediately immersed in iced water and
ð1Þ
then stored at 4 °C for further analyses.
2.5. Determination of salt-soluble protein content
Promatest procedure (NF V03-741) recommended by AFNOR
(2008) as described by Janas et al. (2010a) was applied to study
the influence of treatment on the solubility of SSPs contained in
samples.
at different temperature or heat-treated were extracted using a
ð2Þ
(KH2PO4), 2.1 g of dipotassium phosphate (K2HPO4) and 10 g of so-
dium chloride (NaCl) for 1000 ml.
To determine SSP content of samples, 5.3 ± 0.01 g of corn flour
was introduced in an erlenmeyer with 100 ml of extraction buffer
and agitated for 3 min. The samples were filtered using Whatman
595 1/2 (Germany) filters. The first 20 ml were discarded and the
ð3Þ following 10 ml kept for analysis.
Fifty microlitres of the extraction solution, 40 ll of sample and
3 ml of coomassie blue were put into 4 ml PMMA macro cuvettes
(VWR, Belgium). The cuvettess were agitated slowly and then the
optical density was measured at 595 nm within 15 min.
Six standard solutions corresponding to 10, 20, 30, 40, 50, and
60 mg/100 ml of bovine serum albumin (BSA) from VWR (Belgium)
were used to calibrate the UV-2401 PC UV–Vis recording spec-
trometer from Shimadzu (Japan). All measurements performed
with this method were expressed as mg of equivalent of Bovine
Coomassie blue used was prepared by dissolving 600 mg of coo-
ð4Þ
HCl 0.6 N. The solution continued to be agitated as long as it was
needed to get an optical density of 3.0 ± 0.1, filtered on Whatman
595 1/2 filters (Germany) and stored at room temperature out of
light for 6 weeks maximum.
2.6. Mathematical modeling of the salt-soluble proteins denaturation
ð5Þ
The thermal denaturation of SSPs was described using a first or-
der (Eqs. (6) and (7)) and a second order (Eqs. (8) and (9)) differen-
tial equations presented on Table 1.
Table 1
Different kinetic models used for SSPs denaturation modelization and their analytical
solution.
Kinetic model Differential equation Analytical solution
First order
dP P
¼ k1 P ð6Þ ln ¼ k1 t ð7Þ
dt P0
Second order
dP P  P0
¼ k2 P2 ð8Þ ¼ k2 t ð9Þ
dt PP 0
564 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570
To assess the fitting of the first and the second order kinetic
model presented, the root mean square error (RMSE) was calculated
as:
PN 2
i¼1 ðP exp  Pcal Þ
RMSE ¼ ð10Þ
n moisture content during drying performed at different tempera-
where Pexp and Pcal are, respectively the extractible EBSA observed
experimentally and the EBSA predicted by the model and n the
number of points considered.
The decimal reduction time D (s) which is the time needed to
reduce extractible SSP by 90% (i.e. by one log cycle) was calculated
using the constant rate obtained with the first and second order ki-
netic of hydrothermal treatments according with Janas et al.
(2010a,b):
2:303
D¼ ð11Þ
k
The effect of temperature on the rate of impairment of extract-
ible SSP was calculated by analogy with the classical thermobacte-
riological approach developed by Ball and Olson (1957).
T ref T
D ¼ D0 10 z
ð12Þ
The z coefficient (°C) is the temperature increase necessary to vary
the decimal reduction time by a factor of 10. It was calculated for a
fixed moisture content by linear fit of log D.
2.7. Study of the influence of drying temperature on the sample color
Color measurements were performed in triplicate on samples
(flours) prepared for quantification of SSP following the standard
operating procedure described by AFNOR in NF V03-741, just be-
fore the determination of their extractible SSPs. Corn kernels from
drying process were freeze-dried and ground using a grinder IKA
M20 (Germany) during 3 min in order to obtain flour with average
median diameter less than 500 lm.
A Spectrocolorimeter Hunterlab Miniscan XE Restor VA 3.5 cal-
ibrated with a white standard reference tile was used to measure
the three-dimensional color parameters L⁄a⁄b⁄. A glass cell with a
diameter just close to the nose cone of spectrophotometer, con-
taining sample, was placed above the light source and L⁄, a⁄ and
b⁄ color values were recorded. The Hunter L a b space was used be-
cause it is widely adopted by the food industry and is very effective
in measuring small color differences (Wrolstad and Smith, 2010).
L⁄ value represents the lightness, a⁄ represents the redness and
b⁄ represents the yellowness. Color intensity (DE), chroma (DC)
and hue angle (H) were calculated as described by Wrolstad and
Smith (2010) using the following equations:

DE ¼ ððL Þ2 þ ða Þ2 þ ðb Þ2 Þ0:5 ð13Þ

DC ¼ ðða Þ2 þ ðb Þ2 Þ0:5 ð14Þ
 
a
H ¼ tan1  ð15Þ
b
2.8. Statistical analyses
Statistical analyses were performed using Minitab software
(version 14, MINITAB Inc., State College, PA) for the correlation
analysis and one way ANOVA. The Tukey’s HSD (honestly signifi-
cant difference) test was conducted for pair comparisons when
there was a significant effect at P < 0.05 based on analysis of
variance.
3. Results and discussion
3.1. Influence of drying temperature on moisture content of corn grain
Fig. 1 presents experimental and calculated values of corn grain
tures. High drying temperatures induce rapid decrease of corn
moisture content. The proposed model is satisfactory to describe
the evolution of the corn moisture content.
The effective moisture diffusivities for each drying temperature,
obtained by minimizing the Root Mean Square are presented in
Table 2. The effective moisture diffusivities increase with tempera-
ture. The values obtained are in agreement with those previously
published in the literature. Janas et al. (2010a,b), respectively found
for the same corn variety diffusivities between 0.83  1010 m2 s1
and 2.24  1010 m2 s1 for drying performed between 50 °C and
100 °C. Doymaz and Pala (2003) found moisture diffusivities vary-
ing between 0.94  1010 m2 s1 and 1.15  1010 m2 s1 for a
Turkish corn variety dried between 55 °C and 75 °C.
Prachayawarakorn et al. (2004) stated that the moisture diffusion
inside of the corn kernels depends strongly on the temperature and
also on the instantaneous moisture content of grain. The relationship
between the effective diffusivity and the drying temperature was
modeled by an Arrhenius equation (Fig. 2). The logarithm of the
moisture diffusivity increases linearly with the drying temperature.
The activation energy calculated using the Arrhenius approach
was 464.27 kJ mol1. Prachayawarakorn et al. (2004) also reported
a same trend with an activation energy varying in the range of
500–600 kJ mol1 for corn dried between 90 °C and 170 °C.
As air velocity was approximately set constant in the present
study, the effect of this parameter on corn drying and protein dena-
turation kinetic was not considered for further analysis performed.
3.2. Denaturation kinetic of corn kernel salt-soluble proteins during
drying
Fig. 3 shows the evolution of SSPs content during the drying of
whole corn kernel as observed in the present study.
The extractible SSPs decrease with drying time. The kinetic
could be divided into two phases: an exponential phase during
which SSPs content decreases rapidly and a second phase during
which this parameter tends toward an asymptotic value. A similar
trend was observed by Courtois (1991), Mourad et al. (1996) and
Janas et al. (2010a).
The rate of decrease is important at the beginning of drying
when kernels still have high moisture content. Mourad et al.
(1996) claimed that beyond 70 °C, the denaturation of SSPs occurs
rapidly in the heat-up period of the grains.
As previously observed by Wall et al. (1975), Peplinski et al.
(1994) and Malumba et al. (2008), SSPs are very sensitive to heat
treatment. Newmann et al. (1984) assumed that extensive heat
treatments of native whole corn denature proteins and cause
molecular aggregation through non-convalent hydrophobic inter-
actions and covalently with new intermolecular disulfide cross-
links that contribute to protein insolubility.
Using a sigmoïdal model, Malumba et al. (2009a) observed that
the sensitive temperatures of total SSP extracted by a one-step pro-
cedure from corn kernels, was close to that of starch recovery ob-
served during the wet-milling process. This suggests that the SSPs
solubility index would be appropriate to evaluate the severity of
thermal treatment endured by corn in regard to their wet-milling
performance.
Fig. 4 compares the change of extractible SSP observed experi-
mentally and calculated using the first and the second order kinetic
model during dryings performed between 60 °C and 120 °C.
 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570 565

Fig. 1. Experimental and calculated values of moisture content (d.b.) for dryings at 60 °C, 80 °C, 100 °C and 120 °C.

Table 2
3.3. Denaturation of salt-soluble protein during hydrothermal
Effective moisture diffusivity and residual error for dried corn kernel.
treatments
T (°C) Deff (m2 s1) Root mean square (m2 s1)
60 2.41  10 10
2.53  104 The influence of moisture content on the denaturation of SSPs
80 4.34  1010 1.54  104 was assessed through hydrothermal treatments on cornflour at dif-
100 8.13  1010 1.59  104
ferent fixed moisture contents. Fig. 5 present SSP contents as a
120 14.03  1010 6.98  104
Ea 464.27 kJ mol1 function of moisture content and temperature. Results clearly
show that the moisture content greatly influences the denaturation
process. The higher the moisture content, the faster the denatur-
ation occurs.
The D and z coefficients of impairment of extractible SSP were
calculated for different moisture contents and are presented in
Tables 4 and 5. It can be seen that the drop of extractible SSP oc-
curs rapidly at high moisture content environment. Tables 4 and
5 show that the decimal reduction times of extractible SSP (D)
decreases with the increase of the temperature and moisture
content. The z coefficient also decreases with the increase of
the moisture content. The decrease of D with temperature and
moisture content show that the higher the moisture content
and heat treatments temperature, the faster the denaturation of
SSP in corn is. This confirms that the rate of the reaction also de-
pends on the moisture content in corn kernel. The decrease of z
with increasing of moisture content clearly show that in a higher
Fig. 2. Linear relationship between effective moisture diffusivity and temperature. moisture content protein environment, a smaller increase of tem-
perature induces a logarithmic decrease of extractible SSP in
Table 3 presents the denaturation rate (k) and the RMSE of the corn.
kinetic models used to describe the decrease of the extractible SSPs The role of moisture content of protein environment on the
during the drying. The RMSE values of model show that prediction denaturation reaction was not clearly described by the previous
errors are less important using the second order kinetic than the authors who studied the denaturation of corn SSPs during heat
first order. As assumed by Courtois (1991) and Mourad et al. treatments. Mourad et al. (1996) studied the effect of initial mois-
(1996) it can be conclude that the kinetic denaturation of SSPs dur- ture content on the denaturation of SSPs and pointed out that the
ing drying is better forecasted with the second order kinetic than denaturation process is more pronounced for moistest grains.
with the first order model. Janas et al. (2010a) found a good predic- According to these authors, this effect is noticeable only during
tion with a first order model. Van Boekel (2008) stated that there the period corresponding to the increase of grain temperature
are many conflicting results in literature concerning the kinetic and therefore they concluded that the SSPs content do not change
of protein denaturation. These conflicting results are likely due to considerably with the initial moisture content. Janas et al.
different conditions under which denaturation is studied; denatur- (2010a,b) asserted that moisture content has a great influence on
ation temperature or rate are not determined by the protein alone; the salt-soluble denaturation. But none of them assessed clearly
they depends also on the protein environment and the mathemat- the importance of this parameter on the kinetic of SSP
ical model used to fit experimental data. denaturation.
566 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570

Fig. 3. Impact of drying on the denaturation of extractible salt-soluble proteins.

Fig. 4. Comparison of the experimental SSPs extracted from corn kernel with the calculated values by using a first and a second order kinetic model between 60 °C and 120 °C.

Kovács et al. (2005) assumed that when a protein is fully hy-
drated, the potential energy is considerably smoothed. A sufficient
hydration allows proteins to attain their active minimum-energy
conformation in a straightforward and rapid manner. The potential
energy barriers are lowered and smoothed due to the ease with
which water molecules can lubricate the movement of the amino
acid backbone and side groups by the rapid formation and ex-
change of hydrogen bonds. Further studies are still needed for a
good understanding of the effect of moisture content on the dena-
turation of proteins in a complex matrix such as the corn kernel.
 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570 567

Table 3
Denaturation rate (k) and RMSE calculated for first and second order kinetic models.

K (denaturation rate) Ea (kJ mol1)

60 °C 80 °C 100 °C 120 °C
First order model (s1) 0.78  104 2  104 4  104 11  104 470
Second order model (s1) 1.69  104 8.05  104 58  104 2169  104 1263
RMSE for first order (EBSA) 1.19 2.10 2.50 2.25
RMSE for second order (EBSA) 0.84 1.20 0.41 0.22

Fig. 5. Impact of moisture content on the denaturation of SSP in corn kernels.

Table 4
Variation of the D (s) coefficients according to temperature and moisture content.

Kinetic model Temperature Moisture content (d.b.)

4% 17% 25% 33% 61%
First order 60 °C 88,576 16,333 10,515 7550 6141
80 °C 43,452 10,914 6013 5140
100 °C 34,893 2922 1337
120 °C 8137
Second order 60 °C 62,411 8510,71 3323 2463 1436
80 °C 14,042 3510 2674 216
100 °C 14,042 506 191
120 °C 2006

3.4. Influence of corn drying on its color parameters

Table 5
Variation of the z (°C) coefficients according to the temperature and moisture content. The initial and final values of the different color parameters
Kinetic model Moisture content (d.b.) determined on corn flour are summarized on Table 6. Lightness
(L⁄) and color intensity (DE) parameters decrease while redness
4% 17% 25%
(a⁄), yellowness (b⁄), chroma (DC) and hue angle (H) parameters in-
First order 62.5 53.4 44.6
crease during corn drying. L⁄, a⁄ and b⁄ values change gradually
Second order 45.4 33.3 32.2
during drying at 60 °C and 80 °C while changes of these color
568 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570

Table 6
Color parameters at the beginning and the end of drying.

Color parameters Temperature (°C) Time (s) Mean of initial value Mean of final value
a+
L ⁄
60 10,800 85.04 ± 0.09 80.57 ± 0.21b+
80 7200 85.08 ± 0.15a+ 80.48 ± 0.32b
100 3600 85.21 ± 0.57a+ 76.48 ± 0.12b⁄
120 1800 85.07 ± 0.43a+ 72.47 ± 0.19b⁄
a⁄ 60 10,800 5.12 ± 0.11a+ 7.88 ± 0.12b+
80 7200 5.15 ± 0.14a+ 8.58 ± 0.21b
100 3600 5.16 ± 0.15a+ 10.92 ± 0.08b⁄
120 1800 5.15 ± 0.09a+ 12.25 ± 0.18b°
b⁄ 60 10,800 36.30 ± 0.17a+ 40.29 ± 0.11b+
80 7200 36.31 ± 0.17a+ 42.46 ± 0.37b
100 3600 35.52 ± 0.55a+ 47.51 ± 0.21b⁄
120 1800 36.12 ± 0.16a+ 48.09 ± 0.43b⁄
DE 60 10,800 92.61 ± 0.07a+ 90.43 ± 0.23b+
80 7200 92.65 ± 0.10a+ 91.39 ± 0.16b
100 3600 92.47 ± 0.54a+ 90.70 ± 0.52b
120 1800 92.57 ± 0.41a+ 87.83 ± 0.37b⁄
DC 60 10,800 36.66 ± 0.17a+ 41.05 ± 0.10b+
80 7200 36.67 ± 0.16a+ 43.31 ± 0.32b
100 3600 35.90 ± 0.54a+ 48.75 ± 0.20b⁄
120 1800 36.57 ± 0.41a+ 49.63 ± 0.42b°
H 60 10,800 8.03 ± 0.16a+ 11.07 ± 0.18b+
80 7200 8.08 ± 0.23a+ 11.42 ± 0.37b+
100 3600 8.26 ± 0.26a+ 12.94 ± 0.14b
120 1800 8.11 ± 0.16a+ 14.29 ± 0.22b⁄

Means followed by different letters in the same line and different signs in the same column differ significantly according to Tuckey’s test (P < 0.05); n = 3.

parameters observed for flour from corn dried at 100 °C and 130 °C
was abrupt. Özdemir and Devres (2000) reported that the rate of
color changes was significantly affected by temperature and time.
However, with the increase of the temperature, the effect of time
becomes less and less significant. A similar result was found by
Bhattacharya (1996) who shows that an increase in the processing
time during rice parboiling markedly decreased its lightness, and
increase its redness, yellowness, color intensity and chroma.
During drying all L⁄, a⁄, b⁄, DE, DC and H values and extractible
salt-soluble of corn kernels changed through time. Correlation be-
tween SSPs and color parameters measured was assessed. Table 7
presents the Pearson correlation coefficient between extractible
salt-soluble and color parameters independently to the drying
temperature applied.
Jamin and Flores (1998) measured the characteristics of three
different corn dry-milled products (corn grits, corn cones, and corn
flour) and found that the a⁄ and b⁄ values were positively corre-
lated with protein content while the L⁄ value were negatively cor-
related with protein content. They conclude that the tristimulus
parameter could indicate the amount of protein content in the
degermed corn dry-milled products. Similar correlations were
found by Sandhu et al. (2007) between the L⁄, a⁄ and b⁄ values
and the protein content of nine Indian corn varieties from different
origins.
As it can be seen in Fig. 6 most color parameters measured in
the present study change logically when the extractible SSP of
grain decreases. Mathematical models developed for these param-
eters show that the correlation between SSPs content and the color
parameters are more accurately described by logarithmic or expo-
nential models than linear model.
A hypothesis that could justify the results found is the involve-
ment of SSPs in the Maillard reaction and the resulting color devel-
opment. The Maillard reaction is a cascade of reactions that occurs
when reducing sugars are heated in the presence of free amino
group (e.g., amino acids, amines, and proteins). As well as giving
flavor, the Maillard reaction results in various other outcomes: in-
crease in antioxidative capacity, loss of nutritional and functional
properties, and change of color. As the reaction progresses, some
compounds are formed resulting in the development of yellow, or-
ange, and brown colors. The involvement of Maillard reaction
could explain the decrease of L⁄ value and the increase of a⁄ and
b⁄ value and the highest values of correlation coefficients observed
between these parameters and the decrease of extractible SSP from
corn kernels dried with high air temperature.
As it was found, excessive heat treatment leads to protein dena-
turation, decrease of starch recovery and change on color parame-
ters. Then, color parameters could be used as an indirect index to
detect excessive heat, protein denaturation and therefore to esti-
mate the corn millability.
4. Conclusion
Denaturation of corn SSPs during drying was followed using the
Promatest method which is a useful tool to assess excessive heat of
corn grain. In the present study, it was found that temperature;
moisture content and time of processing greatly influence the

Table 7
Correlation coefficients (r) between the SSP contents and the color parameters of dried corn along the drying process.

L a b DE DC H
a 0.932
b 0.939 0.926
DE 0.886 0.742 0.678
DC 0.945 0.939 0.999 0.688
H 0.874 0.977 0.835 0.741 0.853
Total salt-soluble proteins 0.866 0.822 0.856 0.751 0.857 0.790
 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570 569

Fig. 6. Linear and logarithmic relationship between the color parameters (L⁄, a⁄, b⁄, DE, DC and H) and the SSP content.

kinetic denaturation of SSP of corn kernels. The evolution of
extractible SSP content of corn kernels during drying at high tem-
perature is more correctly described with second order kinetic
than with the first order kinetic reaction. As lower moisture con-
tent induced lower rate of protein denaturation, low temperature
should be used at the beginning of corn drying process, to reduced
corn moisture content without denaturing too much SSP. This first
drying period could then be followed by a raise in temperature.
High temperatures drying also modify the Hunter color param-
eters of corn with a high correlation between the lightness, the yel-
lowness, the redness and SSP content. These parameters could be
used as indirect indicators to detect excessive heat. Further inves-
tigations are needed to assess if these parameters correlate with
the millability of corn and to determine components of the corn
kernel which really participate in the development of color during
their drying.
570 S. Odjo et al. / Journal of Food Engineering 109 (2012) 561–570
Finding a useful tool which permits to rapidly assess the milla-
bility of a corn sample remains a great challenge for food process
engineer and more researches are required.
Acknowledgements
Financial support to M. Odjo was supplied by the ‘‘Coopération
Universitaire au Développement (CUD)’’. The authors are grateful
to Mrs. F. Lefebvre, L. Doran, G. Delimme and D. Cortese for their
assistance.
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