Food Chemistry 136 (2013) 1429–1434

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Food Chemistry
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Identification and thermal stability of purple-fleshed sweet potato anthocyanins

in aqueous solutions with various pH values and fruit juices
Li Jie, Li Xiao-ding ⇑, Zhang Yun, Zheng Zheng-dong, Qu Zhi-ya, Liu Meng, Zhu Shao-hua, Liu Shuo,
Wang Meng, Qu Lu
College of Food Science and Technology, Huazhong Agricultural University, Wuhan 430070, China

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

Article history: Thirteen anthocyanins were identified in the purple-fleshed sweet potato cultivar Jihei No. 1. The main
Received 21 July 2012 anthocyanins were 3-sophoroside-5-glucoside derivatives from cyanidin and peonidin, acylated with
Received in revised form 12 September 2012 p-hydroxybenzoic acid, ferulic acid, or caffeic acid. A unique anthocyanin, delphinidin-3,5-diglucoside
Accepted 14 September 2012
was also found. The thermal stability of purple-fleshed sweet potato anthocyanins (PSPAs) followed a
Available online 23 September 2012
first-order kinetics model. Aqueous solutions with various pH (2, 3, 4, 5, and 6) and fruit juices (apple,
pear, grapefruit, orange, tangerine, kiwifruit, and lemon) were coloured with PSPAs. The enrichment
Keywords:
and degradation kinetics of anthocyanins in these matrices were investigated at 80, 90, and 100 °C. A
Anthocyanins
Purple-fleshed sweet potato
higher stability of anthocyanins was obtained in aqueous solutions with pH 3 and 4 and in apple and pear
Identification juices. Moreover, the activation energies for PSPA degradation in aqueous solutions with various pH and
Thermal stability fruit juices ranged from 66.56 kJ/mol to 111.57 kJ/mol and 46.76 kJ/mol to 75.68 kJ/mol, respectively.
pH Ó 2012 Elsevier Ltd. All rights reserved.
Fruit juices

1. Introduction
Nowadays, consumers are increasingly concerned on the safety
of synthetic colourants. Anthocyanins, a group of bioactive flavo-
noid constituents, are the most abundant water-soluble pigments
widely distributed in tubers, petals, leaves, flowers, fruits, and veg-
etables. They are responsible for the wide array of colours ranging
from salmon-pink through red and violet to near-black, which can
be visible to the human eye (Torskangerpoll & Andersen, 2005). No
toxic effects were observed when anthocyanin was used as a nat-
ural colourant in processed foods (Chisté, Lopes, & de Faria,
2010). Furthermore, anthocyanins possess known chemical and
pharmacological properties, such as decreasing capillary perme-
ability and fragility, scavenging for reactive oxygen species, atten-
uating the proliferation of hepatic stellate cells, and improving
visual acuity (Astrid Garzon, 2008; Choi et al., 2011; Ghiselli,
Nardini, Bbldi, & Scaccini, 1998; Wagner, 1985). These factors have
led to an intensified interest in using anthocyanins as food colou-
rants or dietary antioxidants because of their attractive colours
and potential health benefits.
Commercial anthocyanin colourants are mostly derived from
fruits and vegetables, such as red grape, elderberry, blackcurrant,
blackberry, raspberry, black chokeberry, red cabbage, black carrot,
⇑ Corresponding author. Tel.: +86 27 87282027; fax: +86 27 87384670.
E-mail address: lixd@mail.hzau.edu.cn (X. Li).
purple corn, red radish, and purple-fleshed sweet potato (Kırca,
Özkan, & Cemeroğlu, 2006). Purple-fleshed sweet potatoes contain
large amounts of anthocyanins in the roots, with an anthocyanin
content reported to be around 802–1747 mg kg1 fresh weight
(Steed & Truong, 2008). The main anthocyanins in purple-fleshed
sweet potatoes are 3,5-diglucoside derivatives from cyanidin and
peonidin, acylated with p-hydroxybenzoic acid, ferulic acid, or
caffeic acid, respectively (Kim, Kim, Cho, et al., 2012). These acyl-
ated pigments constitute more than 98% of the total anthocyanin
content in both tubers and shoots (Fossen & Andersen, 2000).
Therefore, purple-fleshed sweet potatoes are a good source of
anthocyanin colourants. However, the primary problem with the
application of anthocyanin colourants is their low stability under
varying light, oxygen, temperature, and pH conditions, among
other factors. Therefore, determining and controlling these labile
factors affecting anthocyanins are needed to successfully replace
synthetic colourants.
The thermal processing of foods involves heating to tempera-
tures ranging from 50 °C to 150 °C, depending on the pH of the
product and the desired shelf life (Patras, Brunton, O’Donnell, &
Tiwari, 2010). Several foods or products containing anthocyanins
must be thermally processed, such as by blanching or pasteurisa-
tion, before consumption. These processes can greatly influence
the anthocyanin content in the final products. For example, Turfan,
Türkyılmaz, Yemisß, and Özkan (2011) previously reported that pas-
teurisation caused an 8–14% and 9–13% loss of anthocyanins in
pomegranate juice from the sacs and the whole fruit, respectively.

0308-8146/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2012.09.054
1430 J. Li et al. / Food Chemistry 136 (2013) 1429–1434
Similar results were reported by Volden et al. (2008) in red cab-
bage and by Kechinski, Guimarães, Noreña, Tessaro, and Marczak
(2010) in blueberry. However, only a few studies have investigated
the stability of purple-fleshed sweet potato anthocyanins (PSPAs).
Reyes and Cisneros-Zevallos (2007) investigated the thermal sta-
bility of aqueous anthocyanins from grape, purple carrot, and pur-
ple- and red-fleshed sweet potato at pH 3. Fan, Han, Gu, and Gu
(2008) studied the colour stability of anthocyanins extracted from
fermented purple sweet potato culture at pH 2–7. These studies
were limited in simple aqueous solution models that mainly con-
tain water. This study aims to identify the constituents of PSPAs
and investigate the effect of pH value (2–6) on the thermal stability
of PSPAs in aqueous solutions at 80, 90, and 100 °C. The thermal
stability of PSPAs in complex juice systems is also studied at the
same temperatures. The thermal degradation studies reported in
this paper can be useful in establishing appropriate processing
guidelines.
2. Materials and methods
2.1. Materials and buffer solutions
Purple-fleshed sweet potatoes (Ipomoea batatas L. cultivar Jihei
No. 1) were generously supplied by the Zixin Biological Technology
Co., Ltd. (Huangshi City, Hubei Province, China). The tubers were
washed in cold tap water, cut into chunks of approximately 3 cm,
steamed at 100 °C for 20 min to prevent browning of the flesh,
cooled and sliced into pieces, and then dried in a heated air drier
at 50 °C (Boxun GZX-9070, Shanghai, China). The samples were
pulverized with a disintegrator and sifted through a 40 mesh sieve.
The resulting powder was then placed in a resealable bag and
stored at 4 °C until use. Apples, pears, grapefruits, oranges, tanger-
ines, kiwifruit, and lemons were purchased from a local market in
Wuhan. The preparation of the buffers of different pH values (2, 3,
4, 5, and 6) was based on the method outlined by Robinson (1986).
The pH 1 and pH 4.5 buffers were prepared according to the
method described by Lee, Durst, and Wrolstad (2005).
2.2. Preparation of PSPAs and fruit juices
Purple-fleshed sweet potato powder (200 g) was extracted with
an ethanol/water/hydrochloric acid solution (50:50:0.01, v/v/v; so-
lid–liquid ratio, 1:20) for 24 h at 4 °C in the dark. The supernatant
was subjected to vacuum evaporation to remove the ethanol
(0.1 MPa, 40 °C) after centrifugation at 3000g for 15 min. The con-
centrated solvents were diluted with distilled water and then
loaded onto an AB-8 macroporous resin (Tianjin, China). The
AB-8 macroporous resin was washed with distilled water, and
the absorbed anthocyanins were subsequently recovered with
70% ethanol. The ethanol eluate was concentrated using a rotary
low-pressure evaporator to remove the ethanol and part of the
water content. Afterward, the PSPA concentrate was kept at 4 °C
for LC–MS analysis and thermal stability research. The concentrate
was extracted three times with ethyl acetate and filtered through a
0.22 lm filter before components identification.
The fruits were washed in cold tap water, and then squeezed
using a household juice extractor (Hauswirt HJE800SA, Germany).
The juices were depectinized with pectinase (Biosharp, Korea) at
50 °C for 1.5 h. The juices were centrifuged at 3000g for 15 min,
and the supernatant juices were subsequently filtered through
three layers of filter paper with kieselguhr and stored at 4 °C. The
buffers and juices were coloured with PSPA concentrate (2.5 g con-
centrate/100 ml solution) before the analyses. The analyses were
conducted within 1 week after the fruit juices were prepared.
2.3. HPLC–MS analysis of anthocyanins
High-performance liquid chromatography (HPLC)–diode array
detection (DAD)–mass spectrometry (MS) analyses were per-
formed using an Agilent 1100 Series LC/MSD system, with a diode
array detector (DAD) coupled to a mass spectrometer (Iron Trap
Detector) equipped with an electrospray ionisation interface (ESI,
Agilent). Chromatographic separation was carried out on a ZORBAX
Eclipse XDB-C18 column (5 lm, 250 mm  4.6 mm i.d., Agilent,
USA).
The mobile phases used were 5% formic acid in water (phase
A) and 5% formic acid in water/acetonitrile (1:1, v/v; phase B).
The following gradients were utilised: a gradient of 20–50% B
for 30 min; 50% B for 5 min; a gradient of 50–20% B for 5 min;
and then a final wash with 20% B for 10 min (Kim et al., 2012).
The analysis was conducted at a flow rate of 1 ml/min at a detec-
tion wavelength of 250 nm–600 nm; the preferred wavelength
was 525 nm. Column temperature was set at 30 °C, and injection
volume was 10 ll. MS spectra were recorded in positive ion mode
between m/z 200 and 1200. The major MS parameters were as
follows: capillary voltage, 3000 V; capillary exit, 132.3 V; drying
gas temperature, 325 °C; gas flow, 10 l/min; and nebulizer pres-
sure, 40 psi.
2.4. Degradation studies
The thermal stability of anthocyanins from purple-fleshed
sweet potato in aqueous solutions with various pH values and fruit
juices was studied at 80, 90, and 100 °C. The coloured buffers and
juices (25 ml) were transferred into test tubes. The sample tubes
were capped tightly to avoid evaporation and placed in a thermo-
static water bath preheated to a given temperature. Samples were
removed from the water bath at regular time intervals, rapidly
cooled by dilution with pH 1 and pH 4.5 buffers, and then analysed
for total monomeric anthocyanin content.
2.5. Determination of total monomeric anthocyanin content
The total monomeric anthocyanin content of the samples was
determined according to the pH differential method (Lee et al.,
2005), with minor modification. The method was based on the
anthocyanin structural transformation that occurs when pH
changes. Aliquots of the coloured buffer solutions or fruit juices con-
taining PSPAs were diluted with pH 1.0 and 4.5 buffers, respectively,
and then placed in the dark for 1 h. The absorbance of each solution
was measured after equilibration using a spectrophotometer
(UV-1700; SHIMADZU, Japan) at a wavelength of maximum absorp-
tion (kvis-max) and 700 nm versus a blank cell filled with distilled
water. Absorbance was calculated as Abs = (Akvis-max  A700)pH1.0 
(Akvis-max  A700)pH 4.5, with a molar extinction coefficient of 26900
for cyanidin-3-glucoside. The total monomeric anthocyanin content
was calculated and expressed as cyanidin-3-glucoside equivalents
using the following equation:
Anthocyanin contentðmg=LÞ ¼ Abs  MW  DF  1000=ðe
 LÞ ð1Þ
where Abs is the absorbance; e is the cyanidin-3-glucoside molar
absorbance (26900); L is the cell path length (1 cm); MW is the
molecular weight of anthocyanin (449.2 Da); and DF is the dilution
factor. All measurements were conducted in triplicate.
2.6. Kinetics model of aqueous anthocyanins
Previous studies showed that anthocyanin degradation under
isothermal heating for the juices and concentrates of grape
 J. Li et al. / Food Chemistry 136 (2013) 1429–1434 1431

(Hillmann, Burin, & Bordignon-Luiz, 2011), blackberry (Wang & Xu,
2007), and black carrot (Kırca, Özkan, & Cemeroğlu, 2007) follows
the first-order kinetics (Equation (2)). The first-order reaction ki-
netic rate constants (k) and half-lives (t1/2), i.e., the time needed
to degrade 50% anthocyanins, were calculated using the following
equations:
lnðC t =C 0 Þ ¼ k  t
1
t 1=2 ¼ ln0:5  k
The dependence of the degradation on temperature was deter-
mined by calculating the activation energy (Ea) and temperature
quotient (Q10) using the following equations:
Fig. 1 shows an HPLC chromatogram of anthocyanins from purple-
fleshed sweet potato, where 11 peaks appeared.
The 13 anthocyanins identified from purple-fleshed sweet pota-
to cultivar Jihei No. 1 are listed in Table 1. Cyanidin and peonidin
were the main anthocyanin aglycones, and the glycosylation were
glucose and sophorose. In addition, almost all anthocyanins from
purple-fleshed sweet potato had sugar residues acylated with
ð2Þ
p-hydroxybenzoic acid, ferulic acid, or caffeic acid. Notably, a
delphinidin (delphinidin-3,5-diglucoside), which had never been
ð3Þ previously reported in purple-fleshed sweet potato, was identified.
This unique anthocyanin may be typical only in the purple-fleshed
sweet potato cultivar Jihei No. 1. Fig. 2 shows the structures and
MS spectra of the six anthocyanin compounds in the cultivar.

lnk ¼ lnk0  Ea =RT ð4Þ

Table 1
Q 10 ¼ ðk2 =k1 Þ10=T 2 T 1 ð5Þ
Mass spectrometric data of anthocyanin compounds in purple-fleshed sweet potato
cultivar Jihei No. 1.
where C0 is the initial monomeric anthocyanin content; Ct is the
monomeric anthocyanin content after t hours of heating at a given Peak M+ (m/z) Fragment Anthocyanin
temperature; t1/2 is the half life time; k is the first-order kinetic rate ions (m/z)
constant (h1); k0 is the frequency factor (h1); Ea is the activation 1 773.4 611.2, 449.1, 286.8 Cyanidin-3-sophoroside-5-glucoside
energy (kJ/mol); R is the universal gas constant (8.314 J/mol K); and 2 787.7 625.2, 463.0, 300.8 Peonidin-3-sophoroside-5-glucoside
3 893.9 731.3, 449.1, 286.8 Cyanidin-3-p-hydroxybenzoyl
T is the absolute temperature (Kelvin).
sophoroside-5-glucoside
4 907.5 745.3, 463.1, 300.8 Peonidin-3-p-hydroxybenzoyl
2.7. Other analyzes sophoroside-5-glucoside
5 627.7 465.0, 302.8 Delphinidin-3,5-diglucoside
949.9 787.4, 449.1, 286.8 Cyanidin-3-(600 -feruloyl
The total soluble solids (Brix) of the coloured fruit juices were
sophoroside)-5-glucoside
measured at 20 °C using an Abbe refractometer (Atago, Japan), 6 963.5 801.3, 463.0, 300.8 Peonidin-3-(600 -feruloyl
and pH was measured with a pH metre (Mettler-Toledo, sophoroside)-5-glucoside
Swizerland). 7 936.0 773.3, 449.1, 286.9 Cyanidin-3-(600 -caffeoyl
sophoroside)-5-glucoside
1055.6 893.5, 449.8, 286.8 Cyanidin-3-caffeoyl-p-
3. Results and discussion hydroxybenzoyl sophoroside-5-
glucoside
8 1111.6 950.2, 449.0, 286.8 Cyanidin-3-(600 -caffeoyl-6000 -feruloyl
3.1. Identification of anthocyanins from purple-fleshed sweet potato
sophoroside)-5-glucoside
9 950.0 787.4, 463.1, 300.8 Peonidin-3-caffeoyl sophoroside-5-
Reverse-phase HPLC and MS analysis were used to identify rap- glucoside
idly the anthocyanins from purple-fleshed sweet potato extracts. 10 1070.2 907.6, 463.1, 300.8 Peonidin-3-caffeoyl-p-
The identification was carried out by comparing molecular ions hydroxybenzoyl sophoroside-5-
glucoside
and important fragment ions obtained from MS with those of the
11 1125.7 963.5, 462.9, 300.8 Peonidin-3-(600 -caffeoyl-6000 -feruloyl
studies reported by Li, Wang, Guo, and Wang (2011), Harada, Kano, sophoroside)-5-glucoside
Takayanagi, Yamakawa, and Ishikawa (2004), and Kim et al. (2012).

Fig. 1. HPLC chromatogram of anthocyanins from purple-fleshed sweet potato cultivar Jihei No. 1.
1432 J. Li et al. / Food Chemistry 136 (2013) 1429–1434
Fig. 2. Structures and MS spectra of six anthocyanin compounds from purple-fleshed sweet potato cultivar Jihei No. 1 (Caf, caffeic acid; Fr, ferulic acid; pHB,
p-hydroxybenzoic acid; Glu, glucose; Hex, hexose).
3.2. Physicochemical parameters of coloured buffers and fruit juices
The physical and chemical characteristics of the fruit juices col-
oured with concentrated PSPAs are presented in Table 2. All the
buffers and fruit juices were coloured with the same amount of
PSPA concentrate, thus, the initial monomeric anthocyanin content
of all solutions should be the same in theory. However, the actual
values ranged from 37.2 mg/l to 52.4 mg/l and 32.8 mg/l to
47.6 mg/l in buffers and juices, respectively. The pH values of fruit
juices ranged from 2.23 to 4.22, among which, the lemon juice
exhibited the lowest value. The Brix values ranged from 8.7 to 12.6.
3.3. Thermal degradation kinetics of PSPAs in aqueous solutions with
various pH values
Relative changes in total monomeric anthocyanin content with
reference to control Ln(Ct/C0) as a function of heat treatment time
(h), at pH 2–6, and from 80 °C to 100 °C were observed. The ther-
mal degradation of PSPAs clearly followed the first-order reaction
kinetics model, with determination coefficients (R2) > 0.94
(Table 3). Our results are in agreement with those from the previ-
ously studies, reporting a first-order reaction kinetics model of for
the degradation of monomeric anthocyanins from various sources
(Hillmann et al., 2011; Kırca et al., 2007; Wang & Xu, 2007).
Table 3 shows that pH level had a significant influence on the
thermal stability of PSPAs. An increase in the degradation rate con-
stant k and a corresponding decline in the t1/2 values were ob-
served with increasing heating temperature. At 80 °C, the t1/2
values of PSPAs increased significantly from 41.8 h at pH 2 to
96.3 h at pH 3, and then decreased rapidly to 8.9 h at pH 6. At 90
and 100 °C, the changing tendency of t1/2 values was the same as
with that at 80 °C; however, t1/2 value at pH 3 was just a little high-
er than at pH 4 at these two temperatures. Much bigger t1/2 values
were obtained at pH 3 and pH 4 compared with that at pH 2, indi-
cating that PSPAs were less stable at lower pH values. This result
was in agreement with a previous study, which reported that
anthocyanins from the extracts of red sweet potato, purple corn,
and commercial purple carrot colourant were more resistant under
 J. Li et al. / Food Chemistry 136 (2013) 1429–1434 1433

Table 2 3.4. Thermal degradation kinetics of PSPAs in fruit juices

Analytical data of buffers and juices coloured with PSPAs concentrate.

pH values Anthocyanin Juices pH
of buffers content (mg/l)
2 52.4a Apple 3.57
3 40.5 Pear 4.22
4 37.2 Grapefruit 3.52
5 37.9 Orange 3.38
6 37.2 Tangerine 3.12
Kiwifruit 3.11
Lemon 2.23
a significantly higher than those of others, revealing that anthocy-
As cyanidin-3-glucoside.
98 °C at pH 3 than at pH 1 (Cevallos-Casals & Cisneros-Zevallos,
2004). By contrast, Hou, Qin, Zhang, Cui, and Ren (2011) reported
that increasing the pH from 1 to 6 hastened the degradation of
black rice anthocyanins, which may be due to the different antho-
cyanin structures across species.
Kırca et al. (2007) reported that the t1/2 values of black carrot
anthocyanins diluted with buffers at 70, 80, and 90 °C were 25.1,
10.0, and 6.3 h, respectively, at both pH 3 and pH 4. Wang and
Xu (2007) found that the t1/2 values of blackberry juice anthocya-
nins at 60, 70, 80 and 90 °C were, respectively, 16.7, 8.8, 4.7 and
2.9 at pH 2.86. By comparison, the t1/2 values of PSPAs were
significantly greater than the anthocyanins from black carrot and
blackberry, which clearly indicated that anthocyanins from pur-
ple-fleshed sweet potato were more thermally stable. However,
the research object of the studies of Kırca et al. and Wang and
Xu were concentrated black carrot juice and blackberry juice,
which both contained numerous other ingredients (i.e., ascorbic
acid) that may change the stability of anthocyanins.
The Ea values of PSPAs at pH 2–6 were 99.95, 111.57, 84.87,
66.56, and 89.38 kJ/mol during heating, respectively (Table 3).
High-activation energy reactions are more sensitive to tempera-
ture changes, thus, a substrate in a reaction with a higher activa-
tion energy that tends to be degraded during a smaller
temperature change is less stable (Hou et al., 2011). Therefore,
PSPAs in aqueous solutions with various pH values are susceptible
to temperature elevation during heating. The temperature during
the heat treatment process should be kept as stable as possible
to preserve anthocyanins. Q10 values of 1.90–3.76 at 80–90 °C
and 1.67–2.50 at 90–100 °C were obtained.
Brix Anthocyanin Thermal degradation of anthocyanins from purple-fleshed
content (mg/l) sweet potato in fruit juices followed the first-order reaction
12.6 39.5a kinetics at 80–100 °C, with determination coefficients (R2) > 0.98
10.5 32.8 (Table 4). Our results are in agreement with the previous study
9.4 45.7 by Kırca et al. (2006). Table 4 shows that the t1/2 values of PSPAs
9.5 43.3
at temperatures ranging from 80–100 °C were 32.4, 17.0, and
10.0 37.4
11.5 47.1 8.1 h, respectively, in apple juice, whereas in pear juice, the val-
8.7 47.6 ues were 22.3, 15.4, and 8.2 h, respectively. These values were
anins in these two fruit juices had higher stability than those in
kiwifruit juice and the other four citrus juices. Almost the same
t1/2 values were obtained for PSPA degradation in orange juice
and tangerine juice at 90 °C and in apple juice and pear juice
at 100 °C. Thus, the stability of PSPAs in various fruit juices can
be ranked in the following descending order, as indicated by
the t1/2 values: apple > pear > grapefruit > orange > tangerine >
kiwifruit > lemon.
Cao, Liu, and Pan (2011) reported that the t1/2 values of blood
orange juice anthocyanins at 70, 80, and 90 °C were 8.21, 5.33,
and 2.79 h, respectively, at pH 3.45. Meanwhile, the t1/2 values of
PSPAs in orange juice at 80 °C and 90 °C were 10.3 h and 6.0 h
respectively. The t1/2 values of PSPAs in orange juice were about
twice the values obtained from blood orange juice anthocyanins,
which may be attributed to its large acylated anthocyanin content.
The anthocyanin molecules with complex patterns of glycosylation
and acylation showed remarkable stability to pH changes, heat
treatment, and light exposure (Dangles, Saito, & Brouillard, 1993;
Figueiredo et al., 1996). Therefore, PSPAs can be a good colourant
for producing stable, red-coloured blood orange juice beverages.
Table 4 shows that the t1/2 values of PSPAs in various fruit juices
ranged from 6.2 h to 32.4 h, 4.4 h to 17.0 h, and 2.6 h to 8.2 h at 80,
90, and 100 °C, respectively. Kırca et al. (2006) reported that the
t1/2 values of black carrot anthocyanins at 80 and 90 °C were 10.1
and 5.0 h in apple juice; 7.2 and 4.2 h in grapefruit juice; 7.2 and
5.6 h in lemon juice; 7.2 and 4.2 h in tangerine juice; and 7.2 and
3.9 h in orange juice, respectively. Compared with black carrot
anthocyanins, the PSPAs were more stable in apple, grapefruit,
orange, and tangerine juices, but less stable in lemon juice. Given
the higher stability of PSPAs, the purple-fleshed sweet potatoes

Table 3
Kinetic parameters for the degradation of PSPAs in aqueous solutions with various pH values.

pH k (h1) t1/2 (h) Ea (kJ/mol) Q10

80 °C 90 °C 100 °C 80 °C 90 °C 100 °C 80–90 °C 90–100 °C
2 0.0166 (0.9835)a 0.0453 (0.9996) 0.1028 (0.9956) 41.8 15.3 6.7 99.95 2.73 2.27
3 0.0072 (0.9413) 0.0271 (0.9979) 0.0549 (0.9958) 96.3 25.6 12.6 111.57 3.76 2.03
4 0.0119 (0.9759) 0.0298 (0.9978) 0.0559 (0.9978) 58.2 23.3 12.4 84.87 2.50 1.88
5 0.0268 (0.9962) 0.0539 (0.9975) 0.0902 (0.9958) 25.9 12.9 7.7 66.56 2.01 1.67
6 0.0779 (0.9913) 0.1477 (0.9970) 0.3689 (0.9940) 8.9 4.7 1.7 89.38 1.90 2.71
a
Numbers in parentheses are the determination coefficients.

Table 4
Kinetic parameters for the degradation of PSPAs in fruit juices.

Juice k (h)-1 t1/2 (h) Ea (kJ/mol) Q10

80 °C 90 °C 100 °C 80 °C 90 °C 100 °C 80–90 °C 90–100 °C
Apple 0.0214 (0.9939)a 0.0407 (0.9978) 0.0853 (0.9994) 32.4 17.0 8.1 75.68 1.90 2.10
Pear 0.0311 (0.9974) 0.0451 (0.9984) 0.0844 (0.9990) 22.3 15.4 8.2 54.55 1.45 1.87
Grapefruit 0.0527 (0.9902) 0.0880 (0.9962) 0.1527 (0.9994) 13.2 7.9 4.5 58.24 1.67 1.74
Orange 0.0673 (0.9889) 0.1150 (0.9959) 0.2094 (0.9996) 10.3 6.0 3.3 62.13 1.71 1.82
Tangerine 0.0709 (0.9890) 0.1130 (0.9950) 0.2117 (0.9981) 9.8 6.1 3.3 59.83 1.59 1.87
Kiwifruit 0.0780 (0.9859) 0.1309 (0.9950) 0.2142 (0.9991) 8.9 5.3 3.2 55.34 1.68 1.64
Lemon 0.1123 (0.9989) 0.1568 (0.9998) 0.2642 (0.9972) 6.2 4.4 2.6 46.76 1.40 1.68
a
Numbers in parentheses are the determination coefficients.
1434 J. Li et al. / Food Chemistry 136 (2013) 1429–1434
can also be a better source than black carrots for producing stable
red-coloured juice beverages except with lemon juice.
The pH values of the fruit juices ranged from 2.23 to 4.22
(Table 2); lemon juice had the lowest pH value (pH 2.23). Mean-
while, the worst PSPA stability was found in lemon juice. This
result was in agreement with the conclusions obtained above.
By comparing the t1/2 values of PSPAs in aqueous solutions with
various pH values and fruit juices at all three temperatures, we
concluded that the stability of purple-fleshed sweet potato antho-
cyanins in complex juice systems was significantly lower than in
buffer solutions. The stability of anthocyanins can increase with in-
ter- and intramolecular copigmentation. Giusti and Wrolstad
(2003) reported that the stacking phenomenon of anthocyanins
can protect chromophores against water nucleophilic attack. Aque-
ous fruit juices contain large amounts of compounds that may
serve as copigments for intermolecular association with anthocya-
nins. However, not all compounds enhance copigmentation. For
example, sugars and their degradation products tend to accelerate
the degradation of anthocyanins (Hou et al., 2011). Compared with
buffer solutions, the lower stability of anthocyanins in fruit juices
may be attributed to the detrimental effects of sugar and ascorbic
acid.
The Ea values of PSPAs in fruit juices ranged from 46.76 kJ/mol
to 75.68 kJ/mol during heating at 80–100 °C. Meanwhile, the Ea
values of PSPAs at pH 2–6 which ranged from 66.56 kJ/mol to
111.57 kJ/mol were obtained (Table 3). High-activation energy
reactions are more sensitive to temperature changes; thus, PSPAs
in aqueous solutions with various pH values were more suscepti-
ble to temperature elevation than in fruit juices. Q10 values were
also calculated to describe the sensitivity of pH and juice matrix
to temperature changes. Q10 values of 1.40–1.90 at 80–90 °C and
1.64–2.10 at 90–100 °C in fruit juices were obtained. Higher Q10
values for pH levels indicate that pH values are more sensitive
to temperature elevation than juice matrices.
4. Conclusions
The results from this study provide detailed information on the
composition of PSPAs and the changes in kinetic stability in
aqueous solutions with various pH values and fruit juices over
the entire temperature range of 80–100 °C. Thirteen anchocyanins
were identified in purple-fleshed sweet potato cultivar Jihei No. 1.
Delphinidin-3,5-diglucoside was found in this cultivar. Further-
more, the degradation of PSPAs followed the first-order reaction
kinetics model. The stability of anthocyanins depended on temper-
ature, pH, and solvent matrix. A higher stability of PSPAs was
achieved at pH 3 and 4. Apple juice and pear juice coloured with
PSPAs showed the highest stability during heating at 80–100 °C.
Therefore, PSPAs can be a good colourant for producing red-col-
oured apple and pear juice beverages. However, further studies
on the stability of PSPAs are needed, considering the great poten-
tial of PSPAs to develop functional foods or serve as functional
colourants.
Acknowledgments
The authors would like to thank the Zixin Biological Technology
Co., Ltd. (Huangshi City, Hubei Province, China) for providing raw
purple-fleshed sweet potatoes. The authors are also grateful to
Ms. Xi Xiao-min for her excellent technical assistance.
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