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LWT - Food Science and Technology 72 (2016) 447e456

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LWT - Food Science and Technology


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Effects of modified starches on the processing properties of


heat-resistant blueberry jam
Lu-Lu Zhang, Jing-Nan Ren, Yan Zhang, Jia-Jia Li, Ya-Li Liu, Zi-Yan Guo, Zi-Yu Yang,
Si-Yi Pan, Gang Fan*
Key Laboratory of Environment Correlative Dietology, Ministry of Education, 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: This paper focused on the effects of modified starches on the processing properties of heat-resistant
Received 24 January 2016 blueberry jam. The optimum conditions of bakery jam was studied. The effect of modified starch on
Received in revised form the protection of the jam color was also analyzed by using IR, NMR and X-ray. The results showed that
6 May 2016
the optimal thickening agent was 10% modified corn starch (MS3), and the baking temperature and time
Accepted 7 May 2016
Available online 8 May 2016
were 180  C and 20 min respectively. After adding the modified starch, the bakery jam had good stability
without syneresis, and had good spreadability and texture after baking. The modified starch played an
obviously positive role in the color, baking resistance, WHC, appearance and spreadability of the blue-
Keywords:
Heat-resistant
berry jam. It might be because the addition of modified starch made the jam system form a fine and
Blueberry jam homogeneous network. The results of IR spectra, X-ray diffraction and 1H NMR analysis showed that
Modified starch modified starch and anthocyanins might be held together by hydrogen bonding. And this endowed the
Anthocyanins heat-resistant characteristics of the blueberry jam after the addition of modified starch.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction Endan, 2012). Additionally, the quality of the blueberry jam during
baking is also decided by the baking temperature and time.
Blueberry belongs to the Ericaceae family. The fruit is blue in The jam quality is usually evaluated either objectively through
color, hence the name blueberry. Mature blueberry fruit is dark blue color, textural and rheological or subjectively using sensorial and
and spherical in shape with a particular sweet and sour taste (Pritts computer vision techniques (Basu & Shivhare, 2013; Javanmard,
& Hancock, 1992). During the natural ripening process, fresh fruits Chin, Yusof, & Endan, 2012). The rheological and textural proper-
have a very short shelf life due to their sensitivity to fungal attack ties of fruit jams have been studied widely (Basu, Shivhare, &
and excessive texture softening (Cordenunsi et al., 2005). Jam Raghavan, 2007; Basu & Shivhare, 2010; Basu, Shivhare, Singh, &
production is an excellent way to meet the needs of off-season Beniwal, 2011). Color is, next to texture, rheology and aroma, one
supply for the blueberry products (Scibisz & Mitek, 2009; Terefe, of the most important quality parameters of jam products
Delon, Buckow, & Versteeg, 2015). (Javanmard, Chin, Mirhosseini, et al., 2012; Poiana, Alexa, &
Blueberry jam is a popular food with intermediate moisture Mateescu, 2012). Anthocyanins contribute to the blue color of the
which is prepared by boiling blueberry pulp, sugar, pectin and acid jam. Blueberries have a high content of anthocyanins, while they
(Basu & Shivhare, 2013). The jam is usually used as fillings and are unstable during processing and storage (Martynenko & Chen,
toppings in bread and cake production. This requires great heat 2016; Pilizota, Kopjara, Zupanic, & Balija, 2011). It has reported
resistance of blueberry jam during the baking process of these that modified starch had protective effects to anthocyanin (Dong,
bakery products, in order to prevent the serious deterioration on Liu, Ju, Lin, & Lian, 2015; Liu, Dong, Lian, Wang, & Lv, 2015). There
the quality of the jam. This is highly dependent on the ingredients may be exist hydrogen bonding interaction between polar group of
of the jam, such as the thickener (Javanmard, Chin, Mirhosseini, & anthocyanin and hydroxyl group of starch (Sang-aroon, Saekow, &
Amornkitbamrung, 2012).
Modified starch is produced from natural starch using physical,
enzymatic or chemical treatments with more great properties, such
* Corresponding author.
E-mail address: fangang@mail.hzau.edu.cn (G. Fan).
as heat-resistance. And it is widely used as gelling, thickening,

http://dx.doi.org/10.1016/j.lwt.2016.05.018
0023-6438/© 2016 Elsevier Ltd. All rights reserved.
448 L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456

stabilizing and filling agents in prepared foods (Galanakis, 2.3.2. Determination of anthocyanins content of heat-resistant
Tornberg, & Gekas, 2010; Javanmard, Chin, Mirhosseini, et al., blueberry jam
2012). The addition of modified starch is extremely important to The anthocyanins content was measured using colorimetric
assure that the jam product has a reasonable thick consistency and assay (Fuleki & Francis, 1968). Two grams of blueberry jam were
to help to maintain the quality of jam during heating (Javanmard, fully crushed and transferred to a flask. A 1:4 hydrochloric acid/
Chin, Mirhosseini, et al., 2012). ethanol mixture (40 mL) was added. The flask was covered with a
Blueberries have been applied extensively in baked products rubber plug and placed in a 40  C water bath. The extraction time
such as bread, cakes and cookies, and received much attention due was 2 h. Then, the filtrates were collected in 100 mL volumetric
to their possible health benefits (Beekwilder, Hall, & de Vos, 2005; flask by suction filtration and diluted with hydrochloric acid/
Rodriguez-Mateos, Cifuentes-Gomez, George, & Spencer, 2014). ethanol to volume. The filtrates were measured using spectropho-
However, information on heat-resistant blueberry jam is not well tometer (Shimadzu Corporation, Kyoto, Japan) at 535 nm absor-
documented, and the protection effect of modified starches on bance. Hydrochloric acid/ethanol solution was used as reference.
anthocyanins in blueberry jam has seldom been reported. The aim Each experiments were performed in triplicate. The content of
of the present study was to study the effects of modified starches on anthocyanins was calculated using the following equation:
the processing properties of heat-resistant blueberry jam. The
protection effect of modified starches on anthocyanins in blueberry A535  V  N

jam was also investigated. 98:2  m

where W is the content of anthocyanins (mg/g), A535 is the filtrate


2. Materials and methods absorbance at 535 nm, V is the constant volume of anthocyanin
extracts (mL), m is the mass of jam (g), N is the dilution multiple,
2.1. Materials and 98.2 is the extinction coefficient of anthocyanins at 535 nm.

Fresh blueberries from Xiangyang Baidi Biotechnology Co., Ltd.


2.4. Effects of the modified starch on the qualities of heat-resisting
were harvested at the commercial maturity stage. Immediately
blueberry jam
after harvesting, blueberries were frozen at 18  C until further
use.
The variety of modified starch, baking temperature and times
Modified tapioca starch (MS1, Shanghai Rand starch technology
were determined by the optimum results of the orthogonal tests.
Co., Ltd, Shanghai, China) and modified corn starch (MS2, Ting Hsin
The heat-resistant blueberry jam was made under the condition
International Group, Hangzhou, China) were acetylated distarch
that the amounts of the modified starch were 0%, 10%, 15%, and 20%,
phosphate with great solubility, swelling power and viscosity sta-
respectively. The color, baking resistance, water-holding capacity,
bility at high temperature and low pH value. Another modified corn
appearance and spreadability, and the microstructure of the jam
starch (MS3, Changchun Dahua starch Technology Co., Ltd,
were measured, observed and analyzed.
Changchun, China) was distarch phosphate with low gelatinization
temperature, good emulsibility and water holding capacity. The
2.4.1. Color analysis
modified starches, pectin (Yantai Andeli pectin Co., Ltd., Yantai,
CIELAB color parameters were recorded as L* (brightness), a*
China) and citric acid (Zhengzhou Yunsheng Biological Technology
(red-green chromaticity coordinate), and b* (blue-yellow chroma-
Co., Ltd., Zhengzhou, China) used were of food grade. The solvents
ticity coordinate) using a Color-Flex 45/0 spectrophotometer
(i.e., ethanol, sodium hydroxide, hydrochloric acid, and potassium
(Hunter Associates Laboratory Inc., Reston, VA, USA). C* (chroma)
bromide, Sinopharm Chemical Reagent Co., Ltd., Shanghai, China)
and DE (Chromatic aberration) were calculated using the following
were of analytical reagent grade.
equation (Felice et al., 2004; Sun, Bai, Zhang, Liao, & Hu, 2001).
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2.2. Preparation of heat-resistant blueberry jam
C* ¼ a*2 þ b*2
Blueberries were washed and soaked in water for 20 min. The qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
fruit was blanched in hot water at 100  C for 5e6 min, and then
DE ¼ DL*2 þ Da*2 þ Db*2
cooled quickly. Afterwards, the modified starch, 25% sugar, 1% where DL* is the differences of the brightness before and after
pectin and 0.2% citric acid were added. The mixture was heated baking.
with continuous stirring until the soluble solids content was 40%.
The jams were hot-packed in glass jars, and then were sterilized at Da* and Db* are the differences of the red-green and blue-
100  C for 25 min. yellow chromaticity before and after baking respectively.

2.3. The optimum conditions for the retention of anthocyanins in


the blueberry jam during baking 2.4.2. Baking resistance analysis
Jams (20 g) were evenly filled in a ring mold with a diameter of
2.3.1. Orthogonal experiment 40 mm, and then they were taken out and baked in an oven. The
Orthogonal experiment was conducted to determine the opti- temperatures of the surface and bottom of the oven were set at
mum conditions for the retention of anthocyanins in the blueberry 200  C and 180  C respectively, and the baking time was 12 min.
jam during baking. The different varieties and amounts of modified Baking resistance was calculated using the following equation (Xu
starches, as well as baking time and temperature were the four & Deng, 2013).
factors, which comprised three levels each (Table 1). Based on the
 
result of orthogonal test, the single-factor experiment was con- S
N¼ 2  1  100
ducted by controlling the other three factors. The effects of the S0
amounts of modified starch, baking time and baking temperature
on anthocyanins content were analyzed, respectively. where N is the baking resistance (%), S0 is the bottom area of the
L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456 449

Table 1
Orthogonal test table.

Level A B C D
(The variety of starches) (Amount of starch %) (Temperature/ C) (Time/min)

1 1 10% 160  C 10
2 2 15% 180  C 15
3 3 20% 200  C 20

jam before baking (mm2), and S1 is the bottom area of the jam after 2.5. Effects of the modified starch on anthocyanins of heat-resisting
baking (mm2). blueberry jam

2.5.1. Pre-treatment of resins


2.4.3. Water-holding capacity (WHC) Macroporous resins (AB-8, Sinopharm Chemical Reagent Co.,
Approximately 3e5 g heat-resistant blueberry jams were ob- Ltd., Shanghai, China) were soaked in 95% ethanol for 24 h, and
tained, and were placed in a weighing disk. Then, jams were placed were washed with distilled water. Then the resins were soaked in
into an oven and dried at 80  C. Jams were weighed every hour until 5% NaOH for 12 h, followed by distilled water until pH of the eluent
the weight remained constant. The mass of the baked jam was became neutral. The resins were then eluted with 5% HCl for 12 h,
recorded, and WHC was calculated using the following equation followed by distilled water until the pH of the eluent became
(Huang, Zhou, & Gu, 2009). neutral. Samples of the pretreated resins were drained (Buran et al.,
2014).
G2  G3
WHC ¼  100%
G2  G1 2.5.2. Extraction and purification of blueberry anthocyanins
The blueberries were thawed and homogenised. The juice was
where G1 is the mass of weighing disk (g), G2 is the mass of
mixed with 80% ethanol (including 3% acetic acid) at the ratio of
weighing disk and the jam before drying (g), and G3 is the mass of
1:15. The extraction was performed at 60  C for 1 h. And then the
weighing disk and the jam after drying (g).
mixture was centrifuged at 5000 rpm/min for 10 min to separate
ethanol extract and blueberry residue. The residue was re-extracted
2.4.4. Appearance and spreadability analysis with an additional acidified ethanol and treated as described above.
Appearance and spreadability analysis was performed from the The ethanol extracts were combined.
following two aspects: on the one hand, the color, texture, shape, Pre-treatment of resins (2 g) and 50 mL of ethanol extract were
and appearance of the jams before and after baking were observed added to 150 mL conical flask. The conical flask was sealed and
and recorded, respectively. On the other hand, the jam was used as shaken at 25  C for 12 h (100 rpm/min). Then it was filtered through
fillings and toppings on the bread production. The dough proofing cheese cloth. The obtained resins were soaked in 50 mL of 70%
with jam was conducted under the following conditions: temper- ethanol solution (pH ¼ 2) for desorption under the same shaking
ature, 35  Ce38  C; relative humidity, 80%e85%; and duration, conditions. The ethanol extraction obtained after filtration was
70 min. Then, the bread was put in the oven. The surface and concentrated using a rotary evaporator (Shanghai Yarong Instru-
bottom temperatures of the oven were set at 200  C, and the baking ment Co., Ltd, Shanghai, China) and dried using a freezer dryer
time was 15 min (Huang et al., 2009). The changes of the jam during (Martin Christ, Osterode, Germany) (Gao, Wu, Chen, & Zheng,
baking, such as the peeling, wrinkling, collapsing and spreadability, 2013).
were observed.
2.5.3. Preparation of the mixture of blueberry anthocyanins and
modified starch
2.4.5. Microstructure analysis The blueberry anthocyanins (9 mg) were dissolved in 10 mL
Scanning electron microscopy (SEM) was a technique used to distilled water, and the absorbance value was adjusted to 1 (Dong
directly observe food surface and microstructure at high resolution et al., 2015; Liu et al., 2015). The MS3 (10 g) was dissolved in
(Basu & Shivhare, 2010). A JSM-6390LV SEM (JEOL Ltd., Tokyo, 100 mL distilled water. And then these two solutions were mixed
Japan) was performed to analyze the freeze dried jam samples. The together. The mixture was treated for gelatinization at 90  C for
jams were mounted on aluminum stubs with double face tape and 20 min and dried to constant weight at 60  C. The finally mixture
coated with a thin layer of gold and palladium alloy to make elec- was obtained after grinding and sieving (Liu et al., 2015).
trical conductivity to the sample. The jams were viewed and pho-
tographed on a SEM at an accelerating voltage of 20 KV and 2.5.4. Infrared spectroscopy (IR) analysis
magnifications in 500and 800. Five milligrams of the samples were crushed, and dried at 120  C
The particle diameter was an important physical property that for 30 min. Then, the samples were mixed with 200 mg potassium
can be used to analyze possible changes when modified starch was bromide, and were scanned by an Infrared Spectrum (Thermo
added (Alloncle & Doublier, 1991). Approximately 0.05 g of the Nicolet Corporation, Madison, WI, USA) at 27  C (Lian, Wang,
samples were added to the dispersing agent (10 mL distilled water), Zhang, & Li, 2014; Lian, Zhang, Luo, Wang, & Liu, 2012).
and then the samples were smashed by ultrasonic cell disruptor
(Ningbo Scientz Biotechnology Co., Ltd., Ningbo, China). The parti- 2.5.5. 1H nuclear magnetic resonance (NMR) analysis
cles of the jam were evenly dispersed in the dispersing agent. The The samples were dissolved in deuterium water at 60  C. The
speed of the circulating pump was 50 rpm/min. According to the analysis was conducted by NMR (Varian Technologies, Palo Alto, CA,
principle of the laser light scattering, the software of the computer USA). The analyzing frequencies of H NMR and C NMR were 300.07
processing can obtain the diameter distribution and dates of the and 75.45 MHz, respectively. The angle of rotation was 45 , and the
sample by particle sizes analyzer (Malvern Instruments Ltd., Mal- delay time was 1 s. Chemical shift was traditionally associated with
vern, UK). Each experiments were performed in triplicate. tetramethylsilane (Lian et al., 2014; Lian et al., 2012).
450 L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456

2.5.6. X-ray diffraction (XRD) analysis of modified starch had an obvious effect on the anthocyanin con-
The samples were wrapped in copper and nickel foils. The tent in jam. Similar results were also obtained in other studies.
analysis was conducted by XRD (Bruker Corporation, Karlsruhe, Zhang and Diao (2013) reported that low levels of starches had no
Germany). The angle of diffraction varied from 4 to 40 (Dong significant effects on the protection of anthocyanins in Cinnamo-
et al., 2015). mum burmannii fruit, while a significant effect of high levels of
starches on the protection of anthocyanins was observed. Kopjar,
2.6. Statistical analysis Adamovic, and Pilizota (2011) found that tapioca starch didn’t
have significant influence on anthocyanin content in blackberry
Mean values and standard deviations of experimental data were juice, while the anthocyanin content decreased with the addition of
calculated using MS Excel 2010 (Microsoft Inc., Seattle, WA, USA). waxy maize starch.
Significant differences of the samples were determined by one-way The results also showed that the content of anthocyanins
ANOVA in SPSS Statistics 19.0 software (SPSS Inc., Chicago, IL, USA). increased first and then decreased with the increase of baking
temperature (140e220  C), and it reached the maximum of about
1.25 mg/g at 180  C. Compared with the jam which was not baked
3. Results and discussion
(20  C), the detected anthocyanins decreased sharply after baking
(140e220  C). And this might be the reason of the loss of the water
3.1. The optimum conditions for the retention of anthocyanins in
during baking. While no obvious differences on the anthocyanins
the blueberry jam during baking
contents at different baking temperatures (140e220  C) were
observed. The relative high stability of the anthocyanins might be
3.1.1. Orthogonal experiment
the result of the addition of modified starches. Additionally, the
The anthocyanins content of the bakery jam was the most
stability of anthocyanins, during baking, was also affected by the
important indicator to judge the quality of jam products, thus the
baking time and temperature and the source of heating and types of
anthocyanins content was used as the evaluation indicator
ovens (Gornas et al., 2016). Gornas et al. (2016) also found that the
(Martynenko & Chen, 2016). As shown in Table 2, the influences of
anthocyanins contents in muffins (enriched by black currant
the processing variables on the indicators were determined using
pomace) increased first and then decreased with the increase of
range (R) and level analyses. Results of the range analysis showed
baking temperature (140e220  C). The same results were also ob-
that the effects of the four factors on the retention of anthocyanins
tained in orthogonal experiments. It can be seen that the antho-
were in the following order: the amount of modified
cyanin content affected by baking temperature. In addition, the
starch > baking time > the variety of modified starch > baking
content of anthocyanin in jam was affected by baking time, and
temperature (RB > RD > RA > RC). K represented the importance of
increased with increasing baking time.
different levels of the same factor. The higher the K value was, the
greater effects were obtained at this level of this factor (Kang et al.,
3.2. Effects of the modified starch on the qualities of heat-resisting
2008). The preferred conditions were obtained with the combina-
blueberry jam
tion of the following factors: A3B1C2D3, i.e., modified corn starch
(MS3), 10% of the modified starch, baking time of 20 min, and
3.2.1. Color analysis
temperature of 180  C. Consequently, the modified corn starch
It is well known that the color of a food system depend on the
(MS3) was used for the further study.
physical state, chemical composition and food structure (Basu &
Shivhare, 2013). The effect of the amount of modified starch
3.1.2. Analysis of single-factor experiment (MS3) on the color of heat-resistant blueberry jam was presented in
The effects of the amount of modified starch (MS3), baking Table 4. Whether jam was baked or not, L*, a* and b* of the jam
temperature and time on the anthocyanins content of blueberry increased with increasing amount of MS3. The changes in the C*
jam were shown in Table 3. When the amounts of the MS3 was 10%, and DE of the bakery jam resulted from the corresponding L*, a* and
anthocyanin contents increased significantly (p < 0.05) to the b*. Before baking, the lowest C* value was obtained without adding
maximum content. And the anthocyanin content decreased with modified starch, C* values increased with the addition of modified
the increase of the modified starch. This might be due to the less starch. This illustrated that the color of jam became lighter and
amount of blueberry was added in the jams as a result of increased more colorful after adding the modified starch. After baking, all of
amount of modified starch added. This result was consistent with the values decreased in a certain extent. The decrease of L* and C*
the results of orthogonal experiments. It indicated that the amount values indicated that the jam turned darker.
When the amount of modified starch was 0%, DE value was 1.26,
which was much higher than that obtained after adding modified
Table 2
Result of the orthogonal test. starch. This can be seen that baking technology does indeed affect
the color of jam. While the effect was becoming smaller with the
No. A B C D Content (mg/g)
increase of MS3 due to the decrease of DE value. This showed that
1 1 1 1 1 1.25 the modified starch might play a protective role in the color of heat-
2 1 2 2 2 1.20
resistant blueberry jam. And this was consistent with the analysis
3 1 3 3 3 1.05
4 2 1 2 3 1.28
of chorma. Modified starch contained many hydroxyl groups that
5 2 2 3 1 1.01 can be coupled with substances in jam system to form a more stable
6 2 3 1 2 0.96 structure (Dong et al., 2015). This stable structure could have a good
7 3 1 3 2 1.25 protective effect of the color of bakery jam. Similar results have
8 3 2 1 3 1.25
been also reported in mango jam by Basu et al. (2011).
9 3 3 2 1 1.02

K1 1.16 1.26 1.15 1.09


3.2.2. Baking resistance analysis
K2 1.08 1.25 1.17 1.14
K3 1.17 1.01 1.01 1.19
The effect of the amount of modified starch on the baking
resistance of jam was shown in Table 5. Baking resistance was an
R 0.09 0.25 0.07 0.10
important impact factor on the quality of bakery jam. Good baking
L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456 451

Table 3
Effects of the amount of modified starch (MS3), baking temperature and time on the content of anthocyanins in blueberry jam.

Variables The content of anthocyanin (mg/g)

The amount of modified starch (%) 0 0.57d ± 0.09


10 1.25a ± 0.08
12.5 1.09b ± 0.11
15 0.83c ± 0.08
17.5 0.59d ± 0.09
20 0.53d ± 0.05

Temperature ( C) 20 0.60c ± 0.03


140 1.13b ± 0.10
160 1.21ab ± 0.01
180 1.25a ± 0.08
200 1.22ab ± 0.02
220 1.17ab ± 0.08

Baking time (min) 0 0.60f ± 0.03


10 0.87e ± 0.03
15 0.96d ± 0.06
20 1.25c ± 0.08
25 1.71b ± 0.02
30 1.90a ± 0.02
a, b, c, d, e, f
. Statistical analysis ANOVA (n ¼ 3) at 95% confidence level with same letters indicating no significant difference. The results are expressed as the mean ± the standard
deviation (n ¼ 3).

Table 4
Effect of the amount of modified starch (MS3) on the particle diameter and color of the jam.

No. Amount of modified starch The particle diameter/nm Before baking After baking DE
L*0 a*0 b*0 C*0 L* a* b* C*

1 0 1131.1a ± 95.6 29.84 2.92 1.23 3.17 28.85 2.15 2.15 2.52 1.26
2 10% 824.7b ± 89.0 29.98 3.87 1.11 4.03 30.03 3.34 1.39 3.62 0.60
3 15% 798.6b ± 83.3 30.24 3.98 1.15 4.14 30.25 3.56 1.44 3.84 0.51
4 20% 837.1b ± 69.9 30.71 4.59 1.14 4.73 30.68 4.21 1.36 4.42 0.44
a, b
. Statistical analysis ANOVA (n ¼ 3) at 95% confidence level with same letters indicating no significant difference.

Table 5
Effect of the amount of modified starch (MS3) on the baking resistance and WHC of the jam.

No. The amount of modified starch % The baking resistance% WHC/%

1 0% 235.91d ± 22.14 70.25a ± 1.28


2 10% 190.13cd ± 13.97 64.23b ± 1.18
3 12.5% 156.41c ± 20.02 62.09bc ± 3.03
4 15% 33.56b ± 43.13 59.28cd ± 1.78
5 17.5% 20.97ab ± 14.19 58.50d ± 1.49
6 20% 37.38a ± 9.02 56.89d ± 1.91
a, b, c, d
. Statistical analysis ANOVA (n ¼ 3) at 95% confidence level with same letters indicating no significant difference. The results are expressed as the mean ± the
standard deviation (n ¼ 3).

resistance of jam should present no significant changes in shape, retention of bakery jam, endow the products with good texture and
smooth surface without bubbles, and unchanged bottom area of the taste. Xu and Deng (2013) had also indicated that the addition of
jam after baking. On the contrary, the deformation, collapse and modified starch increased the baking resistance of jam.
moisture loss were appeared after baking in the jam without good
baking resistance (Xu & Deng, 2013). The baking resistance of jam
increased with the increase of modified starch. Without modified 3.2.3. Particle diameter analysis
starch, the jam completely collapsed with hardened texture after The effect of the amount of modified starch (MS3) on the par-
baking. Moreover, the surface of jam had a porous appearance. ticle diameter of jam was shown in Table 4. The granule sizes of
When the amount of modified starch was over 15%, the jams could sample 1e4 were 1131.1, 824.7, 798.6 and 837.1 mm, respectively.
keep the original shape without bubbles. The baking resistance of The particle size of sample 1 (without modified starch) was the
jam obviously increased compared without adding starch largest. A significant difference (p < 0.05) was observed on the
(p < 0.05). This illustrated that modified starch had a positive effect particle size of the jam after the addition of modified starch. While
on baking resistance of jam. When the amount of modified starch no significant differences were found on the particle size in the
was 20%, baking resistance reached to the highest level. The addi- jams with different contents of the modified starch. And this
tion of modified starch to food as thickening agent could enhance indicated that the particle size of jam decreased by adding modified
the acid and heat resistance of food, strengthen molecular binding starch, while the amount of modified starch had no obvious effects
forces and improve food stability. Huang et al. (2009) reported that on the particle size of jam. Depending on its good gelatinization and
modified starch could improve the heat-resisting and the water water holding capacity, modified starch could be homogeneously
dispersed into jam. It provided a steric hindrance effect which
452 L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456

prevented the aggregation of the jam. And this led to the decrease appearance, and the pore became smaller and more uniform with
of the particles size and the increase of the stability of the jam the increase of modified starch. Similar results were also obtained
(Song, 2013). Tan, Cui, Lu, Zhao, and Wang (2014) had also indicated in other studies (Basu et al., 2011; Tan et al., 2014). The swelling of
that the addition of cross-linked acetylated starch (CAS) resulted in the starch granular occurred at high temperature, and then the pore
the decrease of particle size and the increase of particles in apple at particle surface was open. A network structure was formed after
jam. The same results were obtained from the microstructure the penetration of the substances (might be pectin) into the starch
analysis. granules and combined together (Zhao, 2012). Other researchers
also reported the intermolecular binding of pectin and anthocyanin
3.2.4. Water-holding capacity(WHC) analysis (Lin, Fischer, & Wicker, 2016; Padayachee et al., 2013). Basu et al.
The effect of the amount of modified starch (MS3) on the WHC (2011) indicated that the network was formed in fruit jam
of jam was shown in Table 5. A significant difference (p < 0.05) was through hydrogen bonding and hydrophobic interactions.
observed on the WHC after the addition of MS3. The WHC of jam
was affected by the amount of modified starch, and the WHC was 3.3. Effects of the modified starch on anthocyanins of heat-resisting
enhanced with the increase of modified starch. And it reached the blueberry jam
maximum value of about 56.89%, while the amount of modified
starch was 20%. It is reported that modified starch and the sub- 3.3.1. Infrared spectroscopy (IR) analysis
stance (might be pectin) of jam might be held together and form a The IR spectra of blueberry anthocyanins, modified starch
stable molecular structure, and the hydrophilic groups in starch (MS3), and the mixture were shown in Fig. 2(a). Blueberry an-
and these substances in jam combined with water molecule stable, thocyanins had significant infrared absorption in the wave
so that the system had good water holding capacity and stability number of 3030 cm1 and 1800e1600 cm1. These two absorp-
(Zhao, 2012). Chen and Rui (2010) indicated that modified starch tions were the CeH stretching vibration of aromatic ring and C]
could improve the retentiveness and the emulsibility of hen surimi, O stretching vibration of the ketone, respectively. The peak at
and make products to keep good texture and taste. Huang et al. 1000e1200 cm1 was attributable to CeO stretching vibration of
(2009) also reported that the WHC was enhanced gradually with sugar ring. And the peak at 1400e1600 cm1 was benzene skel-
increase of modified starch. eton vibration.
Modified starch (MS3) had a wide and smooth absorption peak
3.2.5. Appearance and spreadability analysis at 3400 cm1. This indicated that OeH stretching vibration might
Before baking, the jam without modified starch had a smooth exist in MS3 and the association of hydroxyl compounds might be
surface with a purple-red color and low flowability before baking. occurred. The peak at 1000e1200 cm1 might be attributed to CeO
The jam thickened with the increase of modified starch (MS3). After stretching vibration (Li et al., 2004). Modified starch had significant
adding 20% modified starch, the jam became blue-purple and infrared absorption in the wave number of 3000e2800 cm1. It was
extremely sticky with a smooth surface. After baking, the surface of CeH stretching vibration of the alkane. Peaks at 1400 cm1 and
jam without modified starch had a porous appearance with a black 1360 cm1 were attributable to the bending modes of HeCeH and
brown color and completely collapsed shape. A continuous black CeH symmetric bending of CH3 (Sit, Misra, & Deka, 2014).
membrane formed gradually on the jam surface when modified When the blueberry anthocyanins was mixed with MS3, the
starch was added. The color of the jam gradually darkened with absorption peak at 3400 cm1 became sharper. This indicated that
increase modified starch, and this was consistent with the result of the free OeH stretching vibration appeared and the association of
jam color analysis. the hydroxyl compounds was reduced in the mixture. Similar re-
When the jam was used as fillings and toppings on the bread, sults were also obtained in other study (Fang, Fowler, Tomkinson, &
the heat-resistant property of the jam changed with the addition of Hill, 2002; Kazuo et al., 1998). Compared with the modified starch,
modified starch after baking. The jam without modified starch the infrared absorption peak at 1000e1200 cm1 of the mixture
became deformed with hardened surface and blackened color, and decreased significantly. And this indicated that the mixture had
lost moisture after baking. Better results were obtained that jam fewer CeO groups. It is reported that the interaction between
was slightly deformed and wrinkled by adding 10% modified starch. starch and other compounds became stronger with decrease of the
And the jam did not show deformation, collapse and water loss CeO groups in starch (Ma, Yu, & Wan, 2006). And it can be see that
after adding 20% modified starch. This result was the same with the an interaction between the modified starch and anthocyanins
result of jam baking resistance analysis. Additionally, the might be occurred in the mixture.
improvement in color of the jam was also observed after the The absorption peak at 1618e1636 cm1 was observed in all
addition of modified starch. Previous studies had proven that the these three samples. This absorption was OeH bending vibration of
modified starch influenced the quality of jam (Huang et al., 2009; water. And it was stronger in the mixture than that in anthocyanins.
Javanmard, Chin, Yusof, et al., 2012; Ramirez-Sucre & Velez-Ruiz, This indicated that the water content increased after the mixing of
2014; Xu & Deng, 2013). That might be because the vibration of anthocyanins and modified starch (Secundo & Guerrieri, 2005;
starch molecules broke the intermolecular hydrogen bridges of the Zhou, Meng, Chen, Zhu, & Yuan, 2014). This might be because
amorphous zones of the granules during heating, and this led to the that the hydroxyl groups in anthocyanins and starch might be
swelling of granules and formed the structure which could improve combined together through hydrogen bond, and it inhibited the
the jam texture (Pineda-Gomez, Coral, Arciniegas, Rorales-Rivera, & formation of hydrogen bond between the hydroxyl groups in
Rodriguez, 2010). starch. These hydroxyl groups could be combined with water
through hydrogen bond, and this led to the retention of the water
3.2.6. Microstructure analysis during baking (Dong et al., 2015).
SEM was employed to investigate the micro-morphology of the
heat-resistant blueberry jam system, and the results were shown in 3.3.2. 1H NMR analysis
Fig. 1. The jams (without modified starch) possessed a smooth The 1H NMR spectra of blueberry anthocyanins and the mixture
surface without obvious network structures. And the structure (blueberry anthocyanins and modified starch (MS3)) were shown
changed obviously with the increase of modified starch (MS3). The in Fig. 2(b) and (c). The chemical shift of the blueberry anthocyanins
structure of the jam showed an obvious network and porous and the mixture were 1.0e5.1 ppm and 3.3e5.2 ppm, respectively.
Fig. 1. SEM images of heat-resistant blueberry jam. (a) addition of 0% modified starch at magnifications in 500; (b) addition of 10% modified starch at magnifications in 500; (c)
addition of 15% modified starch at magnifications in 500; (d) addition of 20% modified starch at magnifications in 500; (e) addition of 0% modified starch at magnifications in
800; (f) addition of 10% modified starch at magnifications in 800; (g) addition of 15% modified starch at magnifications in 800; (h) addition of 20% modified starch at
magnifications in 800.
454 L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456

Fig. 2. IR spectra, 1H NMR and XRD analysis. (a) IR spectra of blueberry anthocyanins, modified starch (MS3), and the mixture (blueberry anthocyanins and modified starch (MS3));
(b) 1H NMR analysis of blueberry anthocyanins; (c) 1H NMR of the mixture; (d) XRD analysis of blueberry anthocyanins, modified starch, and the mixture.

The chemical shift at 4.70 ppm represented the water molecules Huh, Ooya, Sasaki, & Yui, 2001).
(Dong et al., 2015). The water molecules might exist both in an- Based on the results of the IR spectra, X-ray diffraction and 1H
thocyanins and the mixture. While the content of water in the NMR, it can be speculated that modified starch and anthocyanins
mixture was significantly higher than that in anthocyanins after the might be held together by hydrogen bonding. And this might be the
1
H NMR spectra analysis. Similar results were also obtained in the reason that the blueberry jam kept a great color after the addition
IR analysis and in de Graaf, Lammers, Janssen, & Beenackers (1995) of modified starch. The modified starch could play a good color-
study. The chemical shift at 3.40e3.70 ppm represented the hy- protection role in the jam during baking.
droxyl groups. The decrease of the peak height at 3.40e3.70 ppm of
the mixture was observed. And this indicated that the free hydroxyl
groups decreased after the combination of anthocyanins and 4. Conclusions
modified starch through hydrogen bonding.
This paper focused on the effects of modified starches on the
processing properties of heat-resistant blueberry jam. The effects of
3.3.3. X-ray diffraction (XRD) analysis modified starch on the protection of the jam color were also
XRD analysis of blueberry anthocyanins, modified starch (MS3) analyzed by using IR, NMR and X-ray. The results showed that the
and the mixture (blueberry anthocyanins and modified starch optimal thickening agent was 10% modified corn starch (MS3), and
(MS3)) are shown in Fig. 2(d). The diffraction peaks appeared at the baking temperature and time were 180  C and 20 min,
2q ¼ 23 , 33 for anthocyanins. The intensity of the diffraction respectively.
peaks was very high at 2q ¼ 33 . The diffraction peaks of the Whether the jam was baked or not, L*, a* and b* of the jam
modified starch were observed at 2q of 15 , 18 , 20 , 22 and 33 . increased with increasing amount of modified corn starch (MS3).
While the mixture of modified starch and anthocyanins showed The baking resistance and WHC of the jam increased with the in-
peaks at 18 and 20 . No common peaks were observed both in crease of modified starch. These results indicated that the modified
anthocyanins and the mixture. And this might be the reason that starch played an obviously positive role in the color, baking resis-
anthocyanins were embedded in the modified starch. Compared tance, WHC, appearance and spreadability of the blueberry jam.
with the modified starch, the intensity of the diffraction peaks of Additionally, a significant difference (p < 0.05) was observed on the
the mixture had no obvious changes. The disappearance of some particle size of the jam after the addition of modified starch. And
diffraction peaks of the mixture might indicate the formation of a the structure of the jam with modified starch (MS3) showed an
complex (Desai, Olsen, Mallery, Stoner, & Schwendeman, 2010; obvious network structure and porous appearance, and the pore
L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456 455

became smaller and more uniform with the increase of modified 2402e2404.
Javanmard, M., Chin, N. L., Mirhosseini, S. H., & Endan, J. (2012). Characteristics of
starch.
gelling agent substituted fruit jam: studies on the textural, optical, physico-
The obviously protective effects of modified starch on the chemical and sensory properties. International Journal of Food Science and
blueberry anthocyanins were observed. Based on the results of IR Technology, 47, 1808e1818.
spectra, X-ray diffraction and 1H NMR, it can be speculated that Javanmard, M., Chin, N. L., Yusof, Y. A., & Endan, J. (2012). Application of sago starch
as a gelling agent in jam. CyTA-Journal of Food, 10, 275e286.
modified starch and anthocyanins might be held together by Kang, W. L., Wang, Z. W., Zhou, Y., Meng, L. W., Liu, S. R., & Bai, B. J. (2008).
hydrogen bonding. And this might be the reason that the blueberry Factors influencing HPAM solution viscosity prepared by produced water
jam kept a great color after the addition of modified starch. using orthogonal method. Journal of Central South University Technology, 15,
492e495.
Kazuo, O., Isao, Y., Toshiaki, Y., Shin, O., Seichi, R., Yuuko, N., et al. (1998). Studies on
Acknowledgments the retrogradation and structural properties of waxy corn starch. Bulletin of the
Chemical Societ of Japan, 71, 1095e1100.
Kopjar, M., Adamovic, M., & Pilizota, V. (2011). Thermal degradation of anthocyanins
This work was supported by National Natural Science Founda- in blackberry juice with addition of sugars and starches. In 6th international
tion of China (Program No. 31101239), Major Scientific and Tech- congress flour-bread, hrvatska, Opatija, 84e84.
Lian, X., Wang, C., Zhang, K., & Li, L. (2014). The retrogradation properties of
nological Innovation Project in Hubei Province (2015ABA035) and
glutinous rice and buckwheat starches as observed with FT-IR, 13C-NMR and
the Fundamental Research Funds for the Central Universities DSC. International Journal of Biological Macromolecules, 64, 288e293.
(Program No. 2013PY097). Lian, X., Zhang, K., Luo, Q., Wang, C., & Liu, X. (2012). A possible structure of Ret-
rograded maize starch speculated by UV and IR spectra of it and its compo-
nents. International Journal of Biological Macromolecules, 50, 119e124.
References Lin, Z., Fischer, J., & Wicker, L. (2016). Intermolecular binding of blueberry pectin-
rich fractions and anthocyanin. Food Chemistry, 194, 986e993.
Alloncle, M., & Doublier, J. L. (1991). Viscoelastic properties of maize starch/hy- Li, Y. M., Sun, S. Q., Zhou, Q., Qin, Z., Tao, J. X., Wang, J., et al. (2004). Identification of
drocolloid pastes and gels. Food Hydrocolloids, 5, 455e467. American ginseng from different regions using FT-IR and two-dimensional
Basu, S., & Shivhare, U. S. (2010). Rheological, textural, micro-structural and sensory correlation IR spectroscopy. Vibrational Spectroscopy, 36, 227e232.
properties of mango jam. Journal of Food Engineering, 100, 357e365. Liu, L. Z., Dong, S. R., Lian, X. J., Wang, Y. Y., & Lv, J. Y. (2015). Photobleaching and
Basu, S., & Shivhare, U. S. (2013). Rheological, textural, microstructural, and sensory thermostability studies on monascus red pigment absorbed by potato starch.
properties of sorbitol-substituted mango jam. Food and Bioprocess Technology, 6, Science and Technology of Food Industry, 6, 82e85.
1401e1413. Martynenko, A., & Chen, Y. G. (2016). Degradation kinetics of total anthocyanins and
Basu, S., Shivhare, U. S., & Raghavan, G. S. V. (2007). Time dependent rheological formation of polymeric color in blueberry hydrothermodynamic (HTD) pro-
characteristics of pineapple jam. International Journal of Food Engineering, 3, cessing. Journal of Food Engineering, 171, 44e51.
1e10. Ma, X. F., Yu, J. G., & Wan, J. J. (2006). Urea and ethanolamine as a mixed plasticizer
*Basu, S., Shivhare, U. S., Singh, T. V., & Beniwal, V. S. (2011). Rheological, texture and for thermoplastic starch. Carbohydrate Polymers, 64, 267e273.
spectral characteristics of sorbitol substituted mango jam. Journal of Food En- Padayachee, A., Netzel, G., Netzel, M., Day, L., Mikkelsen, D., & Gidley, M. (2013). Lack
gineering, 105, 503e512. of release of bound anthocyanins and phenolic acids from carrot plant cell walls
Beekwilder, J., Hall, R. D., & de Vos, C. H. R. (2005). Identification and dietary and model composites during simulated gastric and small intestinal digestion.
relevance of antioxidants from raspberry. Biofactors, 23, 197e205. Food & Function, 4, 906e916.
Buran, T. J., Sandhu, A. K., Li, Z., Rock, C. R., Yang, W. H. W., & Gu, L. W. (2014). Pilizota, V., Kopjara, M., Zupanic, N., & Balija, N. (2011). Anthocyanin content and
Adsorption/desorption characteristics and separation of anthocyanins and antioxid and activity of reduced-calorie blueberry jams fortified with green tea
polyphenols from blueberries using macroporous adsorbent resins. Journal of or pine bark extracts. Acta Alimentaria, 41, 424e432.
Food Engineering, 128, 167e173. Pineda-Gomez, P., Coral, D. F., Arciniegas, M. L., Rorales-Rivera, A., & Rodriguez-
Chen, J. L., & Rui, H. M. (2010). Optimization of improving the water-holding ca- Garcia, M. E. R. (2010). Role of water in maize starch gelatinization: an study by
pacity of chicken emulsion products by high hydrostatic pressure using differential scanning calorimetry. Ingeniería y Ciencia, 6, 129e141.
response surface methodology. Science & Technology of Food Industry, 31, 73e76. Poiana, M. A., Alexa, E., & Mateescu, C. (2012). Tracking antioxidant properties and
Cordenunsi, B. R., Genovese, M. I., do Nascimento, O. J. R., Hassimotto, N. M. A., dos color changes in low-sugar bilberry jam as effect of processing, storage and
Santos, R. J., & Lajolo, F. M. (2005). Effects of temperature on the chemical pectin concentration. Chemistry Central Journal, 6, 4e4.
composition and antioxidant activity of three strawberry cultivars. Food Pritts, M. P., & Hancock, J. F. (1992). Highbush blueberry production guide. Ithaca, New
Chemistry, 91, 113e121. York, USA: Northeast Regional Agricultural Engineering Service.
De Graaf, R. A., Lammers, G., Janssen, L. P. B. M., & Beenackers, A. A. C. M. (1995). Ramirez-Sucre, M. O., & Velez-Ruiz, J. F. (2014). Effect of formulation and storage on
Quantitative analysis of chemically modified starches by lH-NMR spectroscopy. physicochemical and flow properties of custard flavored with caramel jam.
Starch, 47, 469e475. Journal of Food Engineering, 142, 221e227.
Desai, K. G. H., Olsen, K. F., Mallery, S. R., Stoner, G. D., & Schwendeman, S. P. (2010). Rodriguez-Mateos, A., Cifuentes-Gomez, T., George, T. W., & Spencer, J. P. E. (2014).
Formulation and in vitro-in vivo evaluation of black raspberry extract-loaded Impact of cooking, proving, and baking on the (poly)phenol content of wild
PLGA/PLA injectable millicylindrical implants for sustained delivery of che- blueberry. Journal of Agricultural and Food Chemistry, 62, 3979e3986.
mopreventive anthocyanins. Pharmaceutical Research, 27, 628e643. Sang-aroon, W., Saekow, S., & Amornkitbamrung, V. (2012). Density functional
*Dong, S. R., Liu, L. Z., Ju, Y., Lin, X. H., & Lian, X. J. (2015). Discussion of mechanism theory study on the electronic structure of monascus dyes as photosensitizer
on monascus red pigments with hydroxyls protected by retrograded maize for dye-sensitized solar cells. Journal of Photochemistry and Photobiology A:
amylose and amylopectin. Science and Technology of Food Industry, 12, 302e306. Chemistry, 236, 35e40.
Fang, J. M., Fowler, P. A., Tomkinson, J., & Hill, C. A. S. (2002). The preparation and Scibisz, I., & Mitek, M. (2009). Effect of processing and storage conditions on
characterisation of a series of chemically modified potato starches. Carbohy- phenolic compounds and antioxid and capacity of highbush blueberry jams.
drate Polymers, 47, 245e252. Polish Journal of Food and Nutrition Sciences, 59, 45e52.
Felice, C. D., Vacca, P., Vecchio, A. D., Criscuolo, M., Lozupone, A., & Latini, G. (2004). Secundo, F., & Guerrieri, N. (2005). ATR -FT/IR study on the interactions between
Early postnatal skin colour changes in term newborns with subclinical histo- gliadins and dextrin and their effects on protein secondary structure. Journal of
logical chorioamnionitis. European Journal of Pediatrics, 163, 550e554. Agricultural and Food Chemistry, 53, 1757e1764.
Fuleki, T., & Francis, F. J. (1968). Quantitative methods for anthocyanins. I. Extraction Sit, N., Misra, S., & Deka, S. C. (2014). Characterization of physicochemical, func-
and determination of total anthocyanin in cranberries. Journal of Food Science, tional, textural and color properties of starches from two different varieties of
33, 72e77. taro and their comparison to potato and rice starches. Food Science and Tech-
Galanakis, C. M., Tornberg, E., & Gekas, V. (2010). Dietary fiber suspensions from nology Research, 20, 357e365.
olive mill wastewater as potential fat replacements in meatballs. LWT-Food *Song, X. (2013). Study of the mechanism of hydroxypropyl distarch phosphate in
Science and Technology, 43, 1018e1025. ketchup. Jinan: Qilu University of Technology.
Gao, Z. C., Wu, T., Chen, W., & Zheng, X. D. (2013). Extraction and purification Sun, J. X., Bai, W. B., Zhang, Y., Liao, X. J., & Hu, X. S. (2001). Effects of electrode
research of anthocyanins of blueberry. Food and Fermentation Technology, 49, materials on the degradation spectral characteristics visual colour and antiox-
1e18. idant capacity of cyaniding-3-glucoside and cyaniding-3-sophoroside during
Gornas, P., Juhnevica-Radenkova, K., Radenkovs, V., Misina, I., Pugajeva, I., pulsed electric field PEF treatment. Food Chemistry, 128, 742e747.
Soliven, A., et al. (2016). The impact of different baking conditions on the sta- *Tan, C. P., Cui, B., Lu, Y. M., Zhao, N., & Wang, Y. (2014). Microstructure and rheology
bility of the extractable polyphenols in muffins enriched by strawberry, sour of apple jam as influenced by cross-linked acetylated starch. Starch, 66,
cherry, raspberry or black currant pomace. LWT - Food Science and Technology, 780e787.
65, 946e953. Terefe, N. S., Delon, A., Buckow, R., & Versteeg, C. (2015). Blueberry polyphenol
*Huang, W. F., Zhou, X. S., & Gu, C. (2009). Effect of modified starch on the quality of oxidase: characterization and the kinetics of thermal and high pressure acti-
heat-resisting fruit jam. Modern Food Science and Technology, 25, 924e927. vation and inactivation. Food Chemistry, 188, 193e200.
Huh, K. M., Ooya, T., Sasaki, S., & Yui, N. (2001). Polymer inclusion complex con- Xu, R. X., & Deng, R. J. (2013). The research of baking stable jam. Food Science and
sisting of poly (epsilon-lysine) and a-cyclodextrin. Macromolecules, 34, Technology, 38, 72e76.
456 L.-L. Zhang et al. / LWT - Food Science and Technology 72 (2016) 447e456

Zhang, J., & Diao, S. P. (2013). Influences of food sour agents, sweeteners, and low-sugar jam. Jinan: Shandong Polytechnic University.
tthickeners on the stability of anthocyanin of Cinnamomum burmannii fruit. Zhou, Y., Meng, S. H., Chen, D. Y., Zhu, X. P., & Yuan, H. B. (2014). Structure char-
Science and Technology of Food Industry, 22, 266e270. acterization and hypoglycemic effects of dual modified resistant starch from
Zhao, N. (2012). Research of action mechanism on cross-linked acetylated starch in indica rice starch. Carbohydrate Polymers, 103, 81e86.