Evaluation of Sulforaphane Content in Sulforaphane-Enriched Broccoli During Tray Drying
Evaluation of Sulforaphane Content in Sulforaphane-Enriched Broccoli During Tray Drying
Evaluation of Sulforaphane Content in Sulforaphane-Enriched Broccoli During Tray Drying
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Andrea Mahn
Aldo Saavedra
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Article history:
Received 14 January 2016
Received in revised form
17 March 2016
Accepted 4 April 2016
Available online 6 April 2016
Sulforaphane is a natural anticancer compound found in broccoli that comes from hydrolysis of glucoraphanin. Conversion of glucoraphanin to sulforaphane has been optimized, however, its use as
functional ingredient is limited because sulforaphane is thermo-labile. We investigated the effect of
drying air temperature (60, 70, 80 C) in tray drying of sulforaphane-enriched broccoli on the evolution
of sulforaphane content. Broccoli temperature and sulforaphane content were registered in time. Sulforaphane content proles were adjusted to a rst-order kinetic model, showing acceptable agreement
(r > 0.90). Sulforaphane formation occurred below 40 C; formation and degradation occurred at broccoli
temperature above 40 C, until the low content of glucoraphanin and moisture, prevents reaction. After
that, only sulforaphane degradation was detected. The highest sulforaphane content at X/X0 0.1 was
67.6 mg/100 g DW, obtained with drying air temperature of 70 C, being 4-fold higher than that found in
fresh broccoli, and the highest reported so far in any dehydrated food.
2016 Elsevier Ltd. All rights reserved.
Keywords:
Sulforaphane degradation
Broccoli
Tray drying
Kinetic model
1. Introduction
Sulforaphane is an isothiocyanate that comes from brassicaceae
vegetables, and it is considered to be a powerful natural anticancer
compound (Matusheski et al., 2004; Elbarbry and Elrody, 2011). Its
precursor is glucoraphanin, which is the most abundant glucosinolate in some broccoli cultivars. Among brassicaceae, broccoli has
by far the highest content of glucoraphanin. The hydrolysis of
glucoraphanin to yield sulforaphane (Fig. 1A) proceeds through the
action of myrosinase (EC 3.2.1.147) to give an unstable intermediate,
which can be subsequently converted spontaneously into nitriles,
thiones, thiocyanates or isothiocyanates, depending on the chemical conditions i.e. pH, temperature, presence of Fe2, presence and
activity of epithiospecier protein (ESP) (Gu et al., 2012). Sulforaphane is the main product of the reaction when it proceeds at
neutral pH and when ESP is inactive (Shen et al., 2010). Although
glucoraphanin can be hydrolyzed by myrosinase, which is released
from the myrosin cells of the vegetable during mastication and
digestion in the intestine, the bioavailability of sulforaphane in this
case is rather low, since the chemical conditions in intestine
* Corresponding author.
E-mail address: [email protected] (A. Mahn).
http://dx.doi.org/10.1016/j.jfoodeng.2016.04.007
0260-8774/ 2016 Elsevier Ltd. All rights reserved.
28
Fig. 1. Representation of (A) the enzymatic hydrolysis of glucoraphanin through the action of myrosinase (adapted from Tanongkankit et al. (2011)), and (B) pathway for degradation of sulforaphane to thiourea proposed by Jin et al. (1999).
dehydrated functional
sulforaphane.
ingredient
naturally
enriched
in
29
glucoraphanin H2 O!sulforaphane D
k2
30
dC
A k1 ,CA
dt
(2)
dCB
k1 ,CA k2 ,CB
dt
(3)
dCC
k2 ,CB
dt
(4)
CB
C
k1 k1 t
e
ek2 t A0
ek2 t
CB0
CB0 k2 k1
(5)
Based on results reported by Tanongkankit et al. (2011), moisture content does not affect sulforaphane content during drying;
only the substrate temperature is the dominant variable that determines the evolution of sulforaphane content during the process.
Hence, the rate constants were expressed through the Arrhenius
equation (Eq. (6)), where ki (s1) is the rate constant, k0i is the
frequency factor (s1), Eai is the activation energy (KJ/mol) and T is
the absolute temperature (K).
Eai
ki ki0 ,e R,T
(6)
Table 1
Drying time to achieve moisture ratio (X/X0) of 0.1 and equilibrium moisture ratio of broccoli (as average standard deviation) at different
temperatures. Different superscripts indicate that values are signicantly different (p < 0.05).
Drying temperature ( C)
60
70
80
6.50
4.50
4.25
0.02 0.002a
0.01 0.006a
0.01 0.005a
Fig. 3. Evolution of sulforaphane content and temperature prole in the broccoli bed
during drying at (A) 60 C, (b) 70 C and (C) 80 C. C0 is the sulforaphane content at
t 0.
31
Table 2
Maximum content of sulforaphane (average standard deviation) achieved during drying at different temperatures and the corresponding moisture ratio and drying time. DW
means dry weight. Different superscripts indicate that values are signicantly different (p < 0.05).
Drying temperature ( C)
60
70
80
0.00
0.25
0.25
1.00
0.93
0.62
Maximum in drying
90.6 2.8
125.5 6.2
103.7 0.8
90.6 2.8
148.9 9.1
106.3 5.3
0.0 0.0a
18.9 9.5b
2.25 5.3a
32
Table 3
Sulforaphane content in broccoli at X/X0 0.1 and retention percentage regarding pre-processed broccoli. DW means dry weight. Different superscripts indicate that values are
signicantly different (p < 0.05).
Drying temperature ( C)
Retention
(%)
60
70
80
5.5
4.0
4.0
18.1 1.6
67.6 0.6
43.0 0.8
19.9 1.2a
54.0 3.7c
41.5 5.3b
ki f Tt
(7)
33
Table 4
Arrhenius parameters for estimating the kinetic constants of eqn. (5) as a function of temperature.
Drying temperature ( C)
k01 (s1)
Ea1 (KJ/mol)
k02 (s1)
Ea2 (KJ/mol)
60
70
80
7.27 103
7.84 103
9.67 103
112.3
48.6
49.2
1.94 107
2.83 105
2.23 105
70.4
57.8
58
0.90
0.98
0.98
5. Conclusion
In all the drying runs there was a period where sulforaphane
was simultaneously synthesized and degraded, resulting in two
decreasing stages with different slopes in the sulforaphane content
prole. This period started at broccoli temperature of 40 C, when
sulforaphane degradation began, but simultaneously there was
sulforaphane formation until glucoraphanin and moisture content
allowed it. This happened approximately at broccoli temperature of
50 C, depending on the drying air temperature, and was reected
as a change in the slope of sulforaphane content prole from this
point onwards.
Sulforaphane content increased at the beginning of drying due
to higher availability of glucoraphanin and temperature close to the
optimum of myrosinase. Afterwards it decreased until the end of
the process. The maximum sulforaphane content was obtained
after 15 min drying at drying air temperature of 70 C (148.9 mg per
100 g dry matter). This represents an 18.9% increase with respect to
the initial sulforaphane content, and an 8.5-fold increase with
respect to the fresh vegetable. The highest sulforaphane retention
at X/X0 0.1 was 54%, obtained with drying air temperature of
70 C. This value is 4-fold higher than that found in fresh broccoli,
and the highest reported so far in any dehydrated food.
The model proposed here gave a relatively good agreement with
the experimental data, resulting in correlation coefcients equal or
higher than 0.9. The best t was obtained with drying air temperature of 80 C (r 0.98), representing the sulforaphane evolution
during the complete process in an acceptable way. The model
should be improved in order to attain a better t.
Acknowledgement
Fondecyt Grant 1130384 supported this research.
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