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Food Chemistry 398 (2023) 133938

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

A new pre-gelatinized starch preparing by spray drying and electron beam


irradiation of oat starch
Huishan Shen a, Jiangtao Yu b, Junqing Bai b, Yili Liu a, Xiangzhen Ge a, Wenhao Li a,
Jianmei Zheng a, *
a
Engineering Research Center of Grain and Oil Functionalized Processing in Universities of Shaanxi Province, College of Food Science and Engineering, Northwest A&F
University, 22 Xinong Road, Yangling 712100, Shaanxi, China
b
Yangling Hesheng Irradiation Technologies Co., Ltd., Yangling 712100, Shaanxi, China

A R T I C L E I N F O A B S T R A C T

Keywords: As a green and safe physical technology, irradiation is increasingly used to improve starch properties. In the
Oat starch study, oat starch was pre-gelatinized at 70 ◦ C followed by spray drying. Subsequently, the spray-dried starch
Spray drying (SDS) was exposed to electron beam (e-beam) irradiation at different doses to obtain new pre-gelatinized starch.
Electron beam irradiation
Spray drying caused a decrement in the ratio of long B3 chains and the molecular weight of starch. Spray-dried
Molecular structure
starch (SDS) slightly increased solubility and swelling power than native starch. When SDS was subjected to e-
Physicochemical characteristics
Rheological properties beam irradiation, its solubility and swelling power increased dramatically, but the pasting viscosities, gelatini­
zation temperatures, apparent viscosity, storage modulus (G′ ) and lost modulus (G′′ ) reduced. The depolymer­
ization of starch molecules and the breakage of amylopectin chains might be responsible for changing the
physicochemical properties of e-beam irradiated starch. These results showed that spray drying combined with e-
beam irradiation would potentially produce new pre-gelatinized starch.

1. Introduction gelatinization (Sarifudin, Sholichah, Setiaboma, & Tongta, 2021). The


gelatinization process can cause chemical and physical changes to the
Oat is the fourth main economic crop globally, mainly consumed as starch granules by rearranging the intra- and intermolecular hydrogen
whole-grain foods, and used in animal feed and industrial applications bonds between the water and starch molecules and can destroy the
(Yu et al., 2022). Oat contains protein, dietary fiber, vitamins, phyto­ crystalline structures of starch granules (dos Santos, Franco, & Leonel,
chemicals, and diversity of essential amino acids, which have health 2020). The general technologies for the preparation of PGS include
functions on reducing blood lipids, regulating blood sugar, lowering drum drying, spray drying, extrusion cooking, and microwave method.
cholesterol, and decreasing the occurrence of colon cancer (Falsafi et al., Spray drying is one of the most economical and effective techniques. The
2019). Therefore, oat has gained popularity due to its high nutritional process involves dehydrating atomized fluid droplets in a hot convective
value. medium and instantaneously transforming the droplets into a dried
Starch is the main constituent of oat, and accounts for up to 60 %. powder (Azhar, Hashib, Ibrahim, & Rahman, 2021). Spray-dried PGS
Starch’s multi-scale structure, physicochemical and functional proper­ can keep the granule integrity because it is less damaged by shear and
ties decided its application for various purposes. However, native starch heat (Ma et al., 2022).
is insoluble in cold water, accessible to retrogradation, and has the poor PGS swells rapidly in cold water and exhibits enhanced viscosity and
anti-shear ability, and it does not possess all the required properties for a desirable thickening properties, widely used in food and non-food in­
specific use. Physical, chemical, enzymatic and their combined modifi­ dustries. Wheat noodles substituted with less than 15 % PGS (w/w)
cation of starch are conducted to modulate the structure, enhance the possessed better mouthfeel and textural properties than the noodles
positive features and extend the reach of specific applications. made from native wheat starch (Yousif, Gadallah, & Sorour, 2012). Li
Pre-gelatinized starch (PGS) is a physically modified starch produced et al. (2020) reported that adding pre-gelatinized corn starch improved
by heating starch in excess water at a temperature above the starch the tensile strength of dough sheets and enhanced the smoothness of

* Corresponding author.
E-mail address: zhengjm75@126.com (J. Zheng).

https://doi.org/10.1016/j.foodchem.2022.133938
Received 22 March 2022; Received in revised form 26 July 2022; Accepted 10 August 2022
Available online 12 August 2022
0308-8146/© 2022 Elsevier Ltd. All rights reserved.
H. Shen et al. Food Chemistry 398 (2023) 133938

noodles. To expand the industrial application of PGS, modifying the temperature, the starch sample was irradiated only once by a high-
functional characteristics of PGS using other technology has attracted energy electron linear accelerator (Yangling Hesheng Irradiation Tech­
much attention in recent years (He et al., 2020; Song et al., 2017; Russ, nologies Co., ltd., Shaanxi, China). The electron beam energy was 10.0
Zielbauer, Ghebremedhin, & Vilgis, 2016). MeV, and the power was 150 kW. The irradiation dose was set to 2, 4, 6,
Electron beam (e-beam) irradiation is a novel non-thermal, eco- and 8 kGy, respectively. The irradiated starch samples were named SDS-
friendly, and meager energy consumption technology that has been 2, SDS-4, SDS-6, and SDS-8.
extensively used in food preservation, sterilization, and material modi­
fication (Xue, Zhao, Wen, Cheng, & Lin, 2017). E-beam irradiation is 2.5. Microscopy analysis
produced from an electron accelerator without requiring a radioactive
source (Du et al., 2020). As a result, it exhibits the advantage of conti­ 2.5.1. Scanning electron microscopy (SEM)
nuity, homogeneity, high utilization rate, and no radioactive hazards A speck of starch sample was fixed to a slab and sprayed with a metal
compared to other radioactive source (Manaila et al., 2021). coat. All samples were recorded at an accelerating voltage of 5 kV using
In recent years, studies have shown that e-beam irradiation has been a Nova Nano SEM 450 SEM (FEI, USA).
more efficient in modifying the multi-scale structure and physico­
chemical properties of starch. E-beam irradiation causes the degradation 2.5.2. Confocal laser scanning microscopy (CLSM)
of the starch molecular structure and debranching of amylopectin, The CLSM images were observed as Shen et al. (2021) described. The
resulting in more short, linear-chain molecules (Zhou, Ye, He, Wang, & starch sample (2 mg), APTS solution (10 mmol/L, 4 μL) and sodium
Jin, 2020). In addition, e-beam irradiation significantly decreased the cyanoborohydride (4 μL) were mixed, and put in an oscillation incubator
crystallinity, pasting viscosity, gelatinization temperature, and at 30 ◦ C for 18 h. After washing, the sample was dispersed in a drop of
enthalpy, while increasing the solubility and resistant starch content of the glycerol-water mixture (1:1, v/v) and recorded by a LEICA TCS SP8
starch (Pan, Xing, Zhang, Luo, & Chen, 2020; Du et al., 2020). CLSM (Leica Microsystems ltd., Germany) equipped with 100 × plan
Knowledge about irradiation technology to improve PGS function­ apo/1.4011 oil UV. The excitation wavelength was 488 nm.
ality is scarce. Therefore, the study aimed to prepare a new pre-
gelatinized starch through spray drying and e-beam irradiation of oat
starch. Furthermore, this work evaluated the effect of e-beam irradiation 2.6. Multi-scale structure
on the structural, physicochemical, and functional properties of spray-
dried PGS from a molecular perspective. 2.6.1. Amylose content (AC)
The amylose content was determined by the Megazyme AMYLOSE/
2. Materials and methods AMYLOPECTIN reagent kit (K-AMYL, Megazyme Co. ltd., Wicklow,
Ireland).
2.1. Materials
2.6.2. Amylopectin chain length distribution (CLD)
Oat grains were purchased from a supermarket located in Shaanxi, The CLD of starch was performed by a high-performance anion
China. In addition, 8-amino-1,3,6-pyrenetrisulfonic acid (APTS) and chromatography with a pulsed amperometric detector system (ICS-
sodium cyanoborohydride were purchased from Sigma Chemicals, St. 5000+, Thermo Fisher Scientific, USA) and referred to the method of Ge
Louis, USA. Pullulanase was purchased from Yuanye Biotechnology Co., et al. (2021). The sample (40 mg) was added to 2 mL of 10 mmol/L
ltd. (Shanghai, China). All other chemical reagents were of analytical sodium acetate buffer (pH 4.5) and gelatinized for 5 min. Then 5 μL of
grade. pullulanase was added and hydrolyzed at 50 ◦ C for 24 h. The mixture
was centrifugated at 3000×g for 10 min and the supernatant was diluted
2.2. Starch isolation 50 times. The analytical column was Dionex CarboPac™ PA-100. The
mobile phase was 0.15 mol/L NaOH (A) and 0.5 mol/L sodium acetate
The wet-milling method was applied to isolate oat starch (Xu et al., containing 0.15 mol/L NaOH (B). The gradient eluent was 0–2 min, 60
2017). Oat grains (500 g) were steeped overnight in 1500 mL of 0.45 % % A; 2–10 min, 50 % A; 10–40 min, 40 % A; 40–60 min, 20 % A.
Na2S2O5 solution and ground in a blender (HX-PB9289A, AUX, Foshan
Haixun Electric Appliances Co., ltd) to form a slurry. The homogenate 2.6.3. Molecular weight (Mw)
was filtered to remove the fibrous impurities and centrifuged at 2000×g According to the method of Ge et al. (2021), the Mw was determined
for 10 min. The starch cake was re-washed with water after removing by high-performance liquid chromatography system (HPLC, Waters,
the upper protein layer. The white starch cake was dried in an oven for Model 410, MA). About 20 mg of starch sample was dissolved in 1 mL of
24 h at 45 ◦ C. The native starch was named NS. 0.1 mol/L NaNO3 solutions and gelatinized for 5 min. The HPLC was
performed using an Ultrahydrogel™ LInear column (300 × 7.8 mm,
2.3. Preparation of pre-gelatinized starch Waters, Tokyo, Japan) and a differential refractive index detector (600E,
Waters, USA). The injection volume was 20 μL, and the mobile phase
The method of Fu, Wang, Li, and Adhikari (2012) was used to pro­ was 0.1 mol/L NaNO3 with a 0.6 mL/min flow rate.
duce pre-gelatinized starch. The starch suspension (10 %, w/v) was
prepared with 40 ◦ C distilled water, and stirred in a 70 ◦ C water bath for 2.6.4. X-ray diffraction (XRD)
10 min. The starch slurry was dried using a spray dryer (SD-Basic, The crystalline characteristic was performed by an X-ray diffrac­
LabPlant, Britain) with an inlet temperature of 170 ◦ C and an outlet tometer (Ultima IV, Rigaku Corporation, Japan), operating at 40 kV and
temperature of 50 ◦ C. The feed rate was 0.6 L/h. The atomizing air 40 mA. All samples were scanned at a diffraction angle (2θ) range of 4-
pressure and flow rate were 4 bars and 70 m3/h. The aspirator rate was 60◦ and a 0.02◦ step size.
set to 100 %. The spray-dried starch sample was named SDS.
2.7. Physicochemical properties
2.4. Electron beam irradiation
2.7.1. Solubility and swelling power
E-beam irradiation was conducted following the method of Shen The starch suspension (2 %, w/v) was heated at 50 to 90 ◦ C for 30
et al. (2022). Each SDS sample (50 g) was packed in a polyethylene min. The solubility and swelling power were calculated as the previous
pouch (8 cm × 9 cm) and placed on a conveyor belt. At room method by Sun et al. (2022).

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H. Shen et al. Food Chemistry 398 (2023) 133938

2.7.2. Pasting properties Curves of the storage modulus (G′ ) and loss modulus (G′′ ) versus strain
Starch (3 g) and 25 g of distilled water were mixed well in an were recorded to obtain the linear viscoelasticity region.
aluminum canister. Then the starch suspension was carried out using a Dynamic viscoelastic properties: The frequency sweeps were set from
Rapid Visco Analyzer (RVA-4500, Perten Instruments, Sweden). The 0.1 to 100 rad/s within the linear viscoelastic strain region (2 % strain).
time–temperature profile was: heated from 50 to 95 ◦ C at a rate of 12 ◦ C/ The elastic modulus (G′ ) and loss modulus (G′′ ) were recorded.
min, held at 95 ◦ C for 2.5 min, then cooled to 50 ◦ C at the same rate. Steady shear analysis: After the dynamic oscillatory analysis, the
resulting paste was held for 120 s at 25 ◦ C. The shear stress of the
2.7.3. Thermal properties samples was conducted over the shear rate of 0–300 s− 1. The strain was
Starch (3 mg) was added to 9 μL of distilled water and sealed in an 2 %. The flow curves (viscosity versus shear rate) were fitted using the
aluminum pan. The sample was heated from 20 to 100 ◦ C at a heating power law model:
rate of 10 ◦ C/min. The nitrogen gas flow was 50 mL/min.
η = K(γ)n− 1 .
2.7.4. Rheological properties
where η is the apparent viscosity (Pa⋅s); K is the consistency coefficient
The starch suspension (6 %, w/v) was gelatinized at 100 ◦ C for 30
(Pa⋅sn); γ is the shear rate (s− 1); n is the flow behavior index.
min with constant stirring. The cooled starch paste was transferred onto
the plate of the HR-1 Rheometer (TA Instruments, USA) equipped with a
2.8. Statistical analysis
40 mm parallel plate (gap = 1 mm). The constant temperature of all tests
was 25 ◦ C.
The reported results were statistically analyzed with the Duncan test
Dynamic strain sweep: The linear viscoelasticity region was deter­
using SPSS 21.0 (SPSS Inc., Chicago, IL, USA) and expressed as mean ±
mined by a dynamic strain sweep, which was performed over a strain
standard deviation. Statistical significance was set to p < 0.05.
range of 0.01 %–100 % at an angular frequency of 5 rad/s and 25 ◦ C.

Fig. 1. Scanning electron micrographs (SEM) and confocal laser scanning micrographs (CLSM) images of native, spray-dried and irradiated oat starch.

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3. Results and discussion involved starch source, spray dryer type, pre-gelatinization tempera­
ture, inlet temperature, etc.
3.1. Morphology observation E-beam irradiation remarkably decreased the AC compared to SDS,
and the AC reduced along with the irradiation dose increased. The
Most native oat starch granules exhibited irregular or polygonal current finding was consistent with previous research (Luo et al., 2019).
shapes, and a minority of oat starch showed an oval shape (Fig. 1). They This may be because the free radicals destroyed the starch macromole­
were smooth in appearance with no apparent fissures. As presented in cules and degraded the amylose chains, which decreases the binding
Fig. 1, spray-dried starch (SDS) granules showed folds and wrinkles on ability of amylose and iodine and causes lower AC (Kumar et al., 2017).
the surface, and the center of the granules displayed a hollow structure.
During the pre-gelatinization stage, starch granules absorbed water and 3.3. Amylopectin chain length distribution
swollen under high temperature and agitation. Upon spray drying, the
swollen granules became wrinkled and shrunken (dos Santos, Franco, Amylopectin is the main component with a highly branched struc­
Mischan, & Leonel, 2019). ture in starch. The amylopectin chains generally fall into A, B, and C
E-beam irradiation did not alter the starch granule surface structure chains. Each amylopectin molecule has a single C chain, which carries
(Fig. 1). The phenomenon was consistent with e-beam irradiated quinoa the single reducing-end group. B-chains are further subdivided into B1,
and waxy corn starch (Du et al., 2020; Zhou, Ye, He, Wang, & Jin, 2020). B2, and B3 chains. Short chains (A and B1 chains) form a double helix
However, Pan, Xing, Zhang, Luo, and Chen (2020) observed that the structure that is participated in crystal formation in the starch granules
surface morphology of rice starch was not destroyed by low dose e-beam (Bertoft, 2017). The amylopectin chain profiles play an important role in
irradiation. In contrast, small fissures occurred on the starch surface at influencing starch’s physicochemical and functional properties.
high dose irradiation (10 kGy). The change of starch granular micro­ Native oat starch displayed a major peak at the degree of polymer­
structure upon e-beam irradiation is dose-dependent. An irradiation ization (DP) of 9 and a subsidiary peak at the DP of 39, and the largest
dose lower than 8 kGy might be relatively weak to produce apparent DP was 47 (Fig. S1). As shown in Table 1, SDS possessed 45.10 % of A
morphological changes in the starch granule. chains, 37.51 % of B1 chains, 13.84 % of B2 chains, and 3.55 % of B3
CLSM is an effective technique to analyze the internal structure of chains, respectively. After e-beam irradiation, the chain length distri­
starch granules, such as growth rings and channels. APTS is a fluores­ bution of amylopectin shifted to a shorter chain direction (Fig. S1).
cence probe that could react with the reducing end of starch molecules Compared to SDS, irradiated starch showed a higher proportion of A
and exhibit bright fluorescence. Native starch had a dark core in the chains (52.90 %–57.81 %) and reduced levels of B1 chains (30.46 %–
hilum (Fig. 1). Other regions of starch granules exhibited strong fluo­ 34.20 %), B2 chains (10.71 %–11.23 %), and B3 chains (0.87 %–2.44
rescence, which implied that oat starch’s hilum contains less amylose. %). This may be attributed to the degradation of long starch chains
SDS sample showed lower fluorescence intensity, and some starch induced by irradiation, releasing more liner short chains (Pan, Xing,
granules lost their intact morphology (Fig. 1). The phenomenon Zhang, Luo, & Chen, 2020). Moreover, the free radicals cleaved the
revealed that SDS was partially gelatinized and disrupted its crystalline glycosidic linkages of starch molecules, hence, the amylopectin chains
structure. The fluorescence intensity of starch became enhanced after e- transformed into short chain fractions. A similar finding was noticed for
beam irradiation (Fig. 1). The reason is probably that irradiation waxy maize starch, Zhou, Ye, He, Wang, and Jin (2020) observed that
induced the degradation of amylopectin chains and produced low mo­ the amylopectin branched chains become shorter upon e-beam irradia­
lecular weight fractions, consequently increasing the fluorescence tion, and the A chains gradually increased while B chains reduced with
intensity. adding irradiation dose.

3.2. Amylose content (AC) 3.4. Molecular weight

From Table 1, native starch had 31.75 % of AC. Spray-dried starch Starch molecules generally fall into two groups: amylopectin and
(34.44 %) presented a slightly higher AC than native starch. However, amylose. Amylopectin with larger Mw was first eluted from the HPLC
dos Santos, Franco, and Leonel (2020) noticed that spray drying did not system (Peak 1). Subsequently, amylose and other macromolecules with
significantly (p > 0.05) affect the AC of sweet potato starch. Izidoro, smaller Mw were eluted (Peak 2). Native starch presented the Mw of
Sierakowski, Haminiuk, de Souza, and Scheer (2011) reported that the amylopectin and amylose was 144.15 × 105 g/mol and 17.49 × 104 g/
AC of spray-dried green banana starch was lower than the starch dried in mol, respectively, higher than SDS (Table 1). In the pre-gelatinization
an oven. These results suggested that the AC of spray-dried starch process, high temperature promoted the migration of water molecules

Table 1
Amylose content, chain length distribution, molecular weight and crystallinity of native, spray-dried and irradiated oat starch. a, b.

Samples AC (%) Chain length distribution (%) Molecular weight (g/mol) Crystallinity
(%)
A chain (DP B1 chain (DP B2 chain (DP B3 chain (DP ≥ Peak1 (×105) Peak2
6–12) 13–24) 25–36) 37) (×104)

NS 31.75 ± 41.03 ± 0.40d 38.42 ± 0.26a 13.86 ± 0.24a 6.68 ± 0.09a 144.15 ± 17.49 ± 27.86 ± 0.90a
0.07b 0.49a 0.27c
SDS 34.44 ± 45.10 ± 0.34c 37.51 ± 0.05a 13.84 ± 0.26a 3.55 ± 0.04b 80.06 ± 0.39b 9.68 ± 0.19e 27.52 ± 1.19a
0.03a
SDS-2 29.54 ± 57.81 ± 0.18a 30.46 ± 0.40c 10.86 ± 0.37b 0.87 ± 0.08e 63.79 ± 0.19c 14.98 ± 24.52 ± 2.10ab
0.03c 0.31d
SDS-4 29.13 ± 56.15 ± 0.31a 31.81 ± 0.16c 10.71 ± 0.21b 1.33 ± 0.12d 39.91 ± 0.51d 20.69 ± 25.10 ± 0.48ab
0.08d 0.13b
SDS-6 28.78 ± 52.31 ± 0.34b 34.03 ± 0.37b 11.22 ± 0.16b 2.44 ± 0.07c 20.53 ± 0.35e 22.50 ± 22.17 ± 0.47b
0.04e 0.19a
SDS-8 28.68 ± 52.90 ± 0.50b 34.20 ± 0.20b 11.23 ± 0.04b 1.67 ± 0.07d 20.52 ± 0.08e 22.38 ± 20.96 ± 0.95b
0.10e 0.23a
a
AC, amylose content; DP, degree of polymerization.
b
Values with different superscripts within a column were significantly different (p < 0.05).

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into starch granules, which eventually led to the disruption of intra and 3.6. Solubility and swelling power
inter-molecular hydrogen bonds. These changes caused the loss of the
crystalline structure of starch granules and damage to the starch struc­ Solubility and swelling power are crucial properties of starch. From
ture, resulting in decreased molecular weight (dos Santos et al., 2018). Fig. 3, the solubility and swelling power of native starch increased with
E-beam irradiation significantly reduced the Mw of amylopectin, temperature and reached a maximum value at 90 oC. The solubility and
while enhancing amylose compared with SDS. With extended irradia­ swelling power of the SDS sample ranged from 1.01 % to 5.82 % and
tion dose, the Mw of amylopectin decreased from 80.06 × 105 to 20.52 4.28 g/g to 8.69 g/g, respectively, were higher than native starch at each
× 105 g/mol for irradiated starch, whereas the Mw of amylose pro­ temperature point. The crystalline structure of starch granules was dis­
gressively increased from 9.68 × 104 to 22.38 × 104 g/mol. The result rupted during pre-gelatinization because of the breakage of molecular
may be that irradiation caused fragmentation of the amylopectin mol­ hydrogen bonds. The water molecules were easily diffused into starch
ecules and produced small molecules with low Mw, which merged with granules and formed hydrogen bonds with exposed hydroxyl groups.
the amylose molecules (Kerf, Mondelaers, Lahorte, Vervaet, & Remon, Meanwhile, the mobility of starch molecules and the leaching of
2001). Besides, the degradation of amylopectin under irradiation is amylose increased, which increased the solubility and swelling power of
more pronounced than amylose. Similarly, Zhou, Ye, He, Wang, and Jin starch (Fu, Wang, Li, & Adhikari, 2012; dos Santos, Franco, & Leonel,
(2020) observed a decrease of Mw in waxy maize starch, and they re­ 2020).
ported that increasing the irradiation dose broke the starch chains and The solubility of irradiated starch was higher than that of SDS,
produced short, linear-chain molecules. This was proved by the results especially at 90 ◦ C (Fig. 3A). As the dose increased, the solubility of
of chain length distribution in Table 1. samples increased more obviously; the solubility was 23.72 % for SDS-8
at 90 ◦ C. After irradiation, the depolymerization of starch molecules
3.5. Crystalline structure may explain solubility improvement. In addition, amylopectin long
chains were broken into more short chains, which had a greater
As shown in Fig. 2A, native oat starch exhibited a typical A-type hydratability than native starch; thus, the solubility increased (Zhou, Ye,
polymorphic form with intense characteristic peaks at 2θ of 15◦ , 17◦ , He, Wang, & Jin, 2020). Analogously, the solubility was enhanced with
18◦ , 23◦ , and weak peak at 20◦ . The crystallinity of native starch was increasing irradiation dose for quinoa flour, corn, and potato starch
27.86 % (Table 1). Spray drying altered the diffraction pattern of oat upon e-beam irradiation (Du et al., 2020; Kerf, Mondelaers, Lahorte,
starch, showing a tiny peak around 13◦ . Moreover, the peak intensity Vervaet, & Remon, 2001).
occurring at 15◦ , 17◦ , 18◦ , and 23◦ decreased, but the peak value at 20◦ E-beam irradiation slightly elevated the swelling power of SDS
increased. The peak at 20◦ represented the formation of amylose–lipid (Fig. 3B). Irradiation destroyed the constituent of amorphous and crys­
complexes. The phenomenon implied that the crystalline structure of talline domains and damaged the molecular structure of starch granules,
native starch was converted into a non-crystalline form (Fu, Wang, Li, & which expedited the amylose leaching out and promoted the granules
Adhikari, 2012). swelling. According to Singh, Singh, Isono, and Noda (2010), starch
E-beam irradiation has not altered the position of XRD peaks, sug­ granules with higher crystallinity have lower swelling power. The
gesting that the crystalline structure characteristics of SDS remained crystallinity demonstrated the high swelling ability of irradiated starch
intact upon irradiation. However, e-beam irradiated starch had lower (Table 1). Besides, the interaction between the starch chains within the
crystallinity than SDS, ranging from 20.96 % to 24.52 %. And the amorphous and crystalline areas also influences the swelling power.
crystallinity was decreased with the rising irradiation dose. This result Similarly, irradiated chickpea, buckwheat, and potato starches have
may be because of the degradation of starch molecules in the irradiation shown higher swelling capacity than native starch. However, this
process. Besides, starch crystallinity was mainly related to the amylo­ increment was only observed at temperatures below 70 ◦ C. When sub­
pectin branch chains. Therefore, e-beam irradiation caused rapid jected to high temperature (>70 ◦ C), the swelling power reduced
degradation of amylopectin and generated more short chains, resulting significantly for chickpea, buckwheat, and potato starch (Bashir &
in reduced crystallinity. The influence of e-beam irradiation on the Aggarwal, 2017; Verma et al., 2018). Sudheesh et al. (2019) found a
crystallinity was confirmed by these reports on rice (Pan, Xing, Zhang, decrease in the swelling index of kithul starch after irradiation, which
Luo, & Chen, 2020), quinoa (Du et al., 2020), waxy maize (Zhou, Ye, He, gradually reduced with the increase in irradiation dose. The contradic­
Wang, & Jin, 2020), brown rice and milled rice starch (Luo et al., 2019). tory results on swelling power might be related to the irradiation sour­
ces, starch type, irradiation energy, and processing dose.

Fig. 2. XRD patterns (A) and DSC curve (B) of native, spray-dried and irradiated oat starch.

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Fig. 3. Solubility (A) and swelling power (B) of native, spray-dried and irradiated oat starch.

3.7. Pasting properties FV and SB than SDS, suggesting that irradiation made starch less prone
to retrogradation. These findings were consistent with previous studies,
Table 2 listed the pasting properties of oat starch that had undergone which indicated that the pasting viscosities of rice and wheat starch,
spray drying and e-beam irradiation. The peak viscosity (PV), trough quinoa and rice flour decreased induced by e-beam irradiation (Pan,
viscosity (TV), breakdown (BD), final viscosity (FV), and setback (SB) of Xing, Zhang, Luo, & Chen, 2020; Hu, Huang, Yin, Zi, & Wen, 2011; Du
native starch were 3312 cP, 2031 cP, 1281 cP, 3439 cP, and 1409 cP, et al., 2020; Luo et al., 2019). The continuously reduced pasting vis­
respectively. Spray drying decreased the pasting viscosities of starch, cosities suggested that the degradation degree of starch chains was
which may be due to the destruction of the ordered structure of starch positively associated with irradiation dose.
and the rearrangement of amylose and amylopectin. This was following The pasting temperature (GT) of native starch was 94.55 ◦ C, which
dos Santos et al. (2018) report, which observed a reduction in PV, BD, was higher than that of rice (74.33 ◦ C), quinoa (69.40 ◦ C), sorghum
and FV of cassava and Peruvian carrot starches upon spray drying. (75.15 ◦ C), and buckwheat starch (71.80 ◦ C) (Sun et al., 2022; Gao et al.,
PV refers to the swelling ability of starch granules when they begin to 2019). Irradiation did not significantly change the GT of oat starch.
rupture and breakdown and is concerned with the water-binding ca­ However, the greater GT indicated that oat starch showed higher
pacity of starch. The PV of starch decreased after e-beam irradiation and resistance toward swelling and required more energy to disintegrate the
showed a declining trend with increasing doses. The degradation of starch structure than other cereal starch.
starch molecules and the breakage of amylopectin by e-beam irradiation
may explain its reduced PV (Hu, Huang, Yin, Zi, & Wen, 2011). A similar
3.8. Thermal properties
phenomenon was observed in early studies (Bashir & Aggarwal, 2017;
Gul, Singh, & Sonkawade, 2016).
As summarized in Table 2, the onset (To), peak (Tp), and conclusion
Similar to the result of PV, e-beam irradiation reduced the TV, BD,
temperature (Tc) of native starch were 56.62 ◦ C, 61.79 ◦ C, and 68.18 ◦ C,
FV, and SB of starch, and decreased along with the irradiation dose
respectively. The highest gelatinization temperatures (To, Tp, Tc) were
increasing. BD is an indicator of the stability of starch pastes and the
found in SDS, and spray drying reduced the gelatinization temperature
shear resistance in the heating process. The great branching extent and
range (Fig. 2B). Previous studies supported this finding (dos Santos,
high level of short amylopectin chains could explain the lessened BD.
Franco, & Leonel, 2020; Fu, Wang, Li, & Adhikari, 2012). In the pre-
The decrease in BD revealed that irradiation modified starch presented
gelatinization process, water molecules infiltrated the starch granules
enhanced resistance to heat and mechanical agitation (Bashir &
and disrupted the amylopectin chains that comprise the crystalline re­
Aggarwal, 2017). In addition, irradiated starch exhibited lower values of
gions. The rearrangement of the crystalline structure may explain its

Table 2
a, b, c.
Pasting and thermal properties of native, spray-dried and irradiated oat starch.
Samples Pasting properties Thermal properties
o
PV (cP) TV (cP) BD (cP) FV (cP) SB (cP) PT (min) GT ( C) To (oC) Tp (oC) Tc (oC) ΔH (J/g)

NS 3312 ± 2031 ± 1281 ± 3439 ± 1409 ± 6.77 ± 94.55 ± 56.62 ± 61.79 ± 68.18 ± 8.30 ±
5a 52b 57a 11a 63a 0.05a 0.01a 0.39c 0.44c 0.28bc 0.14a
SDS 3176 ± 2285 ± 891 ± 3364 ± 1079 ± 6.63 ± 94.53 ± 62.92 ± 65.57 ± 70.49 ± 2.01 ±
68a 37a 11b 13a 16b 0.14ab 0.04a 0.10a 0.01a 0.13a 0.12b
SDS-2 2129 ± 1277 ± 852 ± 1890 ± 613 ± 6.37 ± 94.85 ± 61.98 ± 65.38 ± 69.49 ± 1.97 ±
35b 22c 13b 49b 27c 0.05b 0.07a 0.26ab 0.37a 1.12ab 0.11b
SDS-4 1663 ± 875 ± 4d 788 ± 1405 ± 530 ± 1c 6.04 ± 94.80 ± 61.43 ± 65.18 ± 69.25 ± 1.86 ±
16c 12bc 6c 0.05c 0.29a 0.03ab 0.52a 0.17abc 0.22b
SDS-6 1351 ± 630 ± 8e 722 ± 1069 ± 440 ± 5.90 ± 94.83 ± 61.49 ± 64.59 ± 68.72 ± 1.86 ±
20d 12bc 31d 23c 0.04c 0.04a 0.80ab 0.33ab 005abc 0.10b
SDS-8 1089 ± 461 ± 629 ± 2c 823 ± 362 ± 5.87 ± 94.65 ± 60.76 ± 63.71 ± 67.31 ± 1.77 ±
30e 28f 12e 16c 0.09c 0.14a 0.16b 0.03b 0.54c 0.07b
a
PV, peak viscosity; TV, trough viscosity; BD, breakdown; FV, final viscosity; SB, setback; PT, peak time; GT, pasting temperature.
b
To, onset temperature; Tp, peak temperature; Tc, conclusion temperature; ΔH, enthalpy.
c
Values with different superscripts within a column were significantly different (p < 0.05).

6
H. Shen et al. Food Chemistry 398 (2023) 133938

improved gelatinization temperatures. 3.9. Rheological properties


SDS had lower ΔH (2.01 J/g) than native starch (8.30 J/g), sug­
gesting that SDS was partially gelatinized. This may be caused by the 3.9.1. Dynamic strain sweep
disorder of amylopectin crystallite in the heating process (dos Santos The dynamic strain sweep was used to define the linear viscoelastic
et al., 2018). Moreover, the wet bulb temperature during spray drying region where the strain response was proportional to the applied stress.
also affects the ΔH, because the hydration and high temperatures cause The linear viscoelastic region for native, spray-dried, and irradiated oat
the loss of the crystalline structure of starch. Romano, Ureta, Guerrero- starch, established by strain sweep experiments, is shown in Fig. 4A. The
Sánchez, and Gómez-Zavaglia (2020) reported that the ΔH of spray- linear viscoelastic region’s upper limit was 10 % for all starch samples.
dried quinoa starch gradually reduced with the increase of the inlet The storage modulus (G′ ) started to decline at a > 10 % strain and the
temperature. lost modulus (G′′ ) increased at a > 10 % strain, indicating the break­
E-beam irradiation markedly decreased the To, Tp, and Tc of the down of starch pastes’ structure beyond this deformation level. There­
starch sample compared to their corresponding native spray-dried fore, the measurement strain value was selected as 2 %, which was
starch. Furthermore, the gelatinization temperatures were reduced within the linear viscoelastic region.
with an increasing irradiation dose (Table 2). The reduction in gelati­
nization temperatures implied that irradiation partially broke the crys­ 3.9.2. Dynamic viscoelastic analysis
talline structure of the starch. Starch granules with a high ratio of long From Fig. 4B and C, the G′ was always higher than G′′ for all samples,
amylopectin chains were more stable, requiring high temperature to indicating that all starch samples exhibit a greater elastic characteristic.
destruction. Thus, the depolymerization of amylopectin chains and The G′ and G′′ of all starch samples progressively increased as the
decreased total crystallinity might contribute to the reduced gelatini­ angular frequency increased. The highest G′ and G′′ were observed in the
zation temperatures. Zhou, Ye, He, Wang, and Jin (2020) and Pan, Xing, SDS sample, suggesting spray drying enhanced the viscoelasticity of
Zhang, Luo, and Chen (2020) observed similar results for waxy corn and starch and formed a strong cross-linkage network. Spray drying
rice starch: decreasing the To, Tp, and Tc when the dose was increased. increased the G′ and G′′ of starch, related to its higher AC. Singh, Singh,
However, e-beam irradiation had no significant influence (p > 0.05) on Kaur, Sodhi, and Gill (2003) reported that the high amylose starch
the ΔH. exhibited higher G′ and G′′ than low amylose. After e-beam irradiation,
the G′ and G′′ reduced was dose-dependent. The starch gel had a weak

Fig. 4. Dynamic strain sweep (A), dynamic viscoelastic properties (B and C) and steady shear (D) of native, spray-dried and irradiated oat starch.

7
H. Shen et al. Food Chemistry 398 (2023) 133938

structure and became soft due to the increased irradiation dose. The Acknowledgements
depolymerization of starch molecules and the scission of amylopectin
chains may be responsible for the lower G′ and G′′ of starch (Li, Shi, Du, This study was financially supported by the National Key R&D Pro­
Dong, & Yu, 2021). Sudheesh et al. (2019) pound comparable drop in G′ gram Subproject of China (2017YFD0401203-01). Additionally, the
and G′′ in irradiated kithul starch. authors would like to thank the instrument shared platform of the Col­
lege of Food Science & Engineering and Life Science Research Core
3.9.3. Steady shear analysis Services of NWAFU, for the assistance in the RVA (Cuicui Ma), DSC (Lu
The apparent viscosity of native, spray-dried, irradiated oat starch Cui), rheometer (Lu Cui), SEM (Kerang Huang) and CLSM (Xiaorui Liu).
under steady shear are shown in Fig. 4D. The apparent viscosity of all
starch samples dropped with increasing shear rate (Fig. 4D), which Appendix A. Supplementary data
revealed that all the samples presented non-Newtonian fluid properties.
With a further increase in shear rate, the molecular conformation Supplementary data to this article can be found online at https://doi.
changed and the starch paste structure decomposed, which resulted in a org/10.1016/j.foodchem.2022.133938.
decrease in viscosity (Vriesmann, Silveira, & Petkowicz, 2009). More­
over, the viscosity of irradiated starches showed a lower value than the References
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