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Accepted Manuscript

High hydrostatic pressure processing for the preparation of buckwheat and tapioca
starch films

Sujin Kim, So-Young Yang, Ho Hyun Chun, Kyung Bin Song

PII: S0268-005X(17)32113-6
DOI: 10.1016/j.foodhyd.2018.02.039
Reference: FOOHYD 4298

To appear in: Food Hydrocolloids

Received Date: 21 December 2017


Revised Date: 19 February 2018
Accepted Date: 20 February 2018

Please cite this article as: Kim, S., Yang, S.-Y., Chun, H.H., Song, K.B., High hydrostatic pressure
processing for the preparation of buckwheat and tapioca starch films, Food Hydrocolloids (2018), doi:
10.1016/j.foodhyd.2018.02.039.

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ACCEPTED MANUSCRIPT

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Buckwheat Tapioca starch

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Starch
extraction

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Buckwheat starch

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Thermal TE
High hydrostatic
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processing pressure
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Preparation of the BS and TPS films


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2 High hydrostatic pressure processing for the preparation of buckwheat and

3 tapioca starch films

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6 Sujin Kim a, So-Young Yang a, Ho Hyun Chun b, Kyung Bin Song a,*

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8 Department of Food Science and Technology, Chungnam National University,

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9 Daejeon 34134, Republic of Korea,
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b
10 Research and Development Division, World Institute of Kimchi,

11 Gwangju 61755, Republic of Korea,


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19 *Corresponding author.

20 Department of Food Science and Technology, Chungnam National University,

21 Daejeon 34134, Republic of Korea,

22 Tel.: +82 42 821 6723; fax: +82 42 825 2664.

23 E-mail address: kbsong@cnu.ac.kr (K. B. Song).

24
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25 ABSTRACT

26 Buckwheat starch (BS) and tapioca starch (TPS) films were prepared to compare the

27 effect of different gelatinization methods on the physical, optical, and thermal properties of

28 the films. High hydrostatic pressure processing (HPP) at 600 MPa (20 °C, 20 min) and

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29 thermal processing (TP, 90 °C, 20 min) for gelatinization of the starches were used to prepare

30 the films. Consequently, the films prepared using HPP had higher tensile strength and

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31 elongation at break than those prepared using TP regardless of the starch type. In particular,

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32 the BS films prepared using HPP exhibited lower water vapor permeability (2.10 × 10−9 g/m s

33 Pa) and water solubility (11.67%) values than those prepared using TP (3.10 × 10−9 g/m s Pa,

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34 19.85%). Overall, the application of HPP improved the physical properties and water
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35 resistance of both films. Thus, HPP can be used as a method for the preparation of starch

36 films.
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38 Keywords: Buckwheat starch; Tapioca starch; High hydrostatic pressure processing; Physical
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39 properties; Water vapor permeability

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41 1. Introduction

42 Synthetic polymers for packaging materials are widely used, but they are difficult to

43 decompose naturally, causing waste accumulation (Heydari, Alemzadeh, & Vossoughi, 2013).

44 For environmental conservation, various natural materials such as carbohydrates, proteins,

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45 and lipids are used to develop biodegradable films (Song, Lee, Al Mijan, & Song, 2014).

46 Among them, starch is widely used because it is inexpensive and forms odorless and

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47 colorless films (Jiménez, Fabra, Talens, & Chiralt, 2012). However, starch-based films have

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48 some drawbacks, such as high hydrophyilicity and retrogradadation, which make it

49 undesirable for some appliciations.

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50 Among starches, buckwheat starch (BS) belongs to A-type, and its degree of
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51 polymerization (DP) of amylose is 1020 to 1380 (Zhu, 2016). In particular, BS consists of

52 25% amylose and its retrogradation rate is lower than that of corn or wheat starch due to its
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53 low DP and small molecular weight. Despite these advantages, BS has not been extensively
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54 studied as a film-based material. In contrast, tapioca starch (TPS) belongs to C-type and
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55 consists of 18% amylose, and its DP is 3642 (Waterschoot, Gomand, Fierens, & Delcour,

56 2015). TPS is suitable as a film-based material owing to its low cost and high availability
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57 (Ma et al., 2017). The Food and Agriculture Organization (FAO, 2017) reported that tapioca

58 is grown in more than 100 countries with the production of 273 million tons in 2016.
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59 Furthermore, TPS films have been reported to have high transparency and flexibility
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60 (Valencia-Sullca, Vargas, Atarés, & Chiralt, 2017). Thus, starch extracted from buckwheat

61 flour (A-type) and commercial tapioca starch (C-type) were used as film-based materials in

62 this study.

63 Generally, starches are gelatinized using thermal processing (TP). As an alternative,

64 high hydrostatic pressure processing (HPP), which is called cold gelatinization, has also been

65 studied (Hu, Zhang, Jin, Xu, & Chen, 2017; Li, Bai, Mousaa, Zhang, & Shen, 2012). In
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66 contrast to TP, HPP can convert the native granule structure of starch to a gelatinized one.

67 Gelatinization of starch can be achieved more easily using HPP than TP under specific

68 conditions (Hu et al., 2011), and similar results with TP have been reported regarding

69 gelatinization (Vallons, Ryan, & Arendt, 2014). The characteristics of gelatinized starch

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70 using HPP are partially disintegrated granule structure (Vallons & Arendt, 2010), altered

71 crystalline structure (Yang, Gu, & Hemar, 2013), and lower viscosity of starch solution than

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72 that of the heat-gelatinized starch (Song et al., 2017). In particular, the degree of

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gelatinization of starch granules using HPP can be different depending on the type of starch.

74 Specifically, A-type (cereal starches) has the highest sensitivity to HPP, followed by C-type

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75 (legume starches) and B-type (tuber starches) (Li et al., 2011). In case of starch-based films,
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76 moisture content may result in significant changes in their physical properties (Versino,

77 Lopez, Garcia, & Zaritzky, 2016).


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78 Because HPP is a non-thermal processing, it can inhibit moisture loss during the

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processing, leading to changes in the physical properties of the films. Another advantage of

80 HPP is that retrogradation of starches by HPP is slower than that by TP (Li et al., 2012;
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81 Vallons et al., 2010). However, there are no studies on starch films prepared using HPP
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82 instead of TP, although the effect of HPP on the gelatinization of starch has been reported.

83 Therefore, the objective of this study is to prepare different types of starch films using HPP,
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84 and to compare the physical, optical, and thermal properties of the films with those treated
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85 using TP.

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87 2. Materials and methods

88 2.1. Materials

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89 Buckwheat flour was obtained from Pyeongchang, South Korea. Commercial tapioca

90 starch was purchased from Hyungyil Co. (Seoul, South Korea). Glycerol was purchased from

91 Sigma–Aldrich (St. Louis, MO, USA).

92

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93 2.2. Extraction of starch from buckwheat

94 BS was extracted as described by Zhu (2016) with minor modifications. First,

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95 buckwheat flour (100 g) and distilled water (600 mL) were mixed, and the slurries were

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homogenized (12,000 rpm, 5 min) and adjusted to pH 11 with 0.1 N NaOH. The resulting

97 slurries were stirred at 4 °C for 24 h and centrifuged (3,000 × g, 10 min). The pellet was

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98 dissolved in distilled water, neutralized to pH 7 with 1 N HCl, and centrifuged under the
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99 same conditions. The pellet was subsequently dried and passed through an 80-mesh sieve.

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101 2.3. Preparation of the films

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Buckwheat and tapioca starch (3 g) and glycerol (0.9 g) were added to distilled water

103 (100 mL). In the case of TP, the mixture was heated at 90 °C for 20 min with continuous
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104 stirring. In order to prepare the films using HPP, the mixture was stirred at 25 °C for 24 h.
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105 Preliminarily, 300 and 600 MPa were applied during HPP using an Ultra High Pressure

106 Equipment (Model R-201, Chemre System, Inc., Anyang-si, South Korea). However, starch
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107 samples did not exhibit complete gelatinization at 300 MPa. Thus, HPP was applied at 600
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108 MPa under temperature control (max. 24 °C, decreased below 20 °C within 5 min) for 20 min.

109 After the TP or HPP treatment, the filtered film-forming solution (25 mL) was poured onto a

110 glass plate (24 × 30 cm) and dried on a clean bench at 25 °C for 16 h.

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112 2.4. Measurement of mechanical properties

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113 Both tensile strength (TS) and elongation at break (E) of the BS and TPS films were

114 determined using an Instron (Model 4484, Instron Co., Canton, MA, USA) according to

115 ASTM D638-14. All films were cut into a rectangular shape (2.54 x 10 cm), and TS and E

116 were evaluated under the condition of 5 cm of initial grip distance with 50 mm/min of cross-

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117 head speed. Five measurements were recorded.

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119 2.5. Water solubility (WS) and moisture content (MC)

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The WS and MC of the BS and TPS films were determined as described by Lee and

121 Song (2017). The films (2 × 2 cm) were dried at 105 °C for 24 h and the initial weight of the

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122 films was determined. After soaking the films in distilled water (15 mL) with continuous
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123 shaking at 25 °C for 24 h, the remaining films were dried again and weighed (final weight).

124 For the measurement of MC, the films were dried at 105 °C for 24 h and weight loss was
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125 evaluated. Three measurements were recorded.

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127 2.6. Water vapor permeability (WVP)


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128 The WVP of the BS and TPS films was analyzed as described by Yang, Lee, Lee,
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129 and Song (2017). First, a polymethylacrylate cup filled with distilled water (15 mL) was

130 sealed with the film (2 × 2 cm). Afterward, the cup was weighed every hour for 8 h at 25 °C
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131 and 50% relative humidity. Three measurements were recorded.


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133 2.7. Viscosity of film-forming solution

134 The viscosity of film-forming solutions treated with TP or HPP was analyzed

135 according to the method described by Kim et al (2017). The film-forming solutions were

136 prepared and the viscosity was measured in centipoises (cP) at 25 °C using a Brookfield

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137 viscometer (Model DV-1, Brookfield Engineering Labs Inc., Stoughton, MA, USA) with LV

138 spindle No.1. Five measurements were recorded for each sample.

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140 2.8. Optical properties

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141 The color of the films was measured using a colorimeter (Minolta, CR-400, Tokyo,

142 Japan). The L* (lightness), a* (redness), and b* (yellowness) values were determined using

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143 the CIELAB color scale. The opacity of the films was obtained as follows: Opacity =

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144 absorbance at 600 nm/thickness of the film (mm).

145

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146 2.9. Differential scanning calorimetry (DSC) analysis
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147 The thermal property of the BS and TPS films was measured using a differential

148 scanning calorimeter (DSC1; Mettler Toledo, Greifensee, Switzerland). Each sample (10 ± 2
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149 mg) was sealed in a sample pan and heated from 0 to 250 °C at a rate of 10 °C/min.
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151 2.10. Scanning electron microscopy (SEM) analysis

152 The microstructure of the films was examined using an SEM (LYRA3 XMU; Tes-
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153 can Brno, Czech Republic). Secondary electrons were applied to the cross-section of the BS

154 and TPS films with a magnification of 2000×.


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156 2.11. Statistical analysis

157 The experimental results were evaluated using SAS software (Version 9.4, SAS Inst.,

158 Inc., Cary, NC, USA) with Duncan’s multiple range test. p < 0.05 was considered statistically

159 significant. All the data were denoted as mean ± standard deviations.

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161 3. Results and discussion


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162 3.1. Mechanical properties

163 The thickness of the BS films prepared using HPP was slightly larger than those

164 prepared using TP, whereas the TPS films exhibited similar values for the HPP and TP

165 methods (Table 1). Furthermore, both TS and E values increased using HPP as compared to

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166 using TP, regardless of the starch type. In particular, the TS of the BS films prepared using

167 TP and HPP were 13.61 and 18.29 MPa, respectively, and those of TPS films were 24.67 and

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168 26.92 MPa (Table 1). The differences in the physical properties of the films treated using the

169

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TP or HPP treatment can be attributed to different driving forces, leading to the transition of

170 starch crystalline structure during treatment. It has been explained by a hypothesis that

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171 gelatinization via TP is an entropy-driven transition, whereas HPP is a volume-driven
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172 transition (Vallons et al., 2014). In particular, starch crystalline structures can be changed

173 from A- to B-type using HPP (Yang, Chaib, Gu, & Hemar, 2017). The amylopectin structures
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174 of A-type starches are more scattered than those of the B-type starches, and they are

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stabilized by a higher quantity of associated water molecules through van der Waals forces,

176 allowing rearrangements of the helix structure and favoring the B-type structure (Katopo,
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177 Song, & Jane, 2002). Similarly, Basiak, Lenart, and Debeaufort (2017) reported that
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178 structural difference of starches could cause different results regarding film properties. In

179 particular, A-type had a higer sensitivity to HPP than C-type, resulting in different changes
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180 in the physical properties of BS and TPS films by HPP in this study. Furthermore, the films
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181 prepared using HPP had much higher E values than those prepared using TP in the present

182 study (Table 1). The starch films prepared using HPP could maintain higher moisture content

183 in the film matrix than TP, and water could act as a plasticizer in starch-based films (Shaili,

184 Abdorreza, & Fariborz, 2015), leading to improved flexibility and extensibility of the films.

185 The difference of increase in physical properties between BS and TPS films can be associated

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186 with the difference of crystalline type. Overall, the application of HPP positively influenced

187 the physical properties of both BS and TPS films in this study.

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189 3.2. MC and WS

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190 In the films obtained using HPP, higher MC and lower WS were observed compared

191 to the films obtained using TP (Table 2). The MC values of the BS films prepared using TP

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192 and HPP were 12.03 and 15.76%, respectively. Similarly, the corresponding values of the

193

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TPS films were 12.14 and 13.40%, respectively. The films obtained using HPP were prepared

194 without heating, resulting in less loss of water during the preparation of the films. Thus, HPP

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195 maintained higher moisture content of the films compared to TP, causing differences in the
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196 physical, water barrier, morphological, and thermal properties of the films. Similar to our

197 results, okenia films prepared via cold gelatinization with NaOH exhibited higher MC
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198 compared to the films prepared using thermal gelatinization (Romero-Bastida et al., 2005).

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Furthermore, there were significant differences in the WS values of the samples. Noticeably,

200 the WS values of the BS films prepared using TP and HPP were 19.85 and 11.67%,
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201 respectively, and those of the TPS films were 28.53 and 17.53%, respectively, indicating that
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202 the WS of both films decreased with the application of HPP despite higher MC. The decrease

203 in WS might be due to the starch granules remaining after HPP. Papathanasiou, Reineke,
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204 Gogou, Taoukis, and Knorr (2015) reported that helix unwinding was suppressed with the
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205 application of HPP owing to the stabilization of hydrogen bonds, favoring the helix structure.

206 Consequently, some crystalline granule structures could still be maintained after the HPP

207 treatment (Buckow, Heinz, & Knorr, 2007), resulting in low WS of the films. Similarly, a

208 decrease in the WS of corn starch with the application HPP as compared to TP has been

209 reported (Kim, Choi, Kim, & Baik, 2010).

210
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211 3.3. WVP

212 As shown in Fig 1, lower values of WVP were observed for both BS and TPS films

213 with the application of HPP, compared to TP. In particular, the WVP values of the BS films

214 prepared using TP and HPP were 3.10 and 2.10 × 10−9 g/m s Pa, respectively, resulting in a

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215 significant difference (p < 0.05). These results might be due to the enhanced physical

216 properties of the films (Table 1). The relatively denser matrix of the BS and TPS films treated

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217 with HPP could be attributed to the decrease in WVP because water molecules transferred

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through the film could be hindered. Orsuwan and Sothornvit (2017) also reported that lower

219 WVP of banana flour films was due to a denser and compact film matrix, which reduced the

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220 diffusion of water vapor. Similar results were observed for corn-starch-based films (Dai, Qiu,
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221 Xiong, & Sun, 2015). In contrast, there was no statistical difference in the WVP of TPS films

222 prepared using the two treatments. As starches have different physicochemical properties and
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223 crystalline structures depending upon the type of starch, they exhibit different resistance to

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high pressure (Colussi et al., 2018; Katopo et al., 2002). Overall, the starch films prepared

225 using HPP had significantly low or similar values of WVP compared to the films obtained
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226 using TP.


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228 3.4. Viscosity


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229 The film-forming solutions treated with HPP had lower viscosity than those treated
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230 with TP (Table 3). In particular, the viscosity of the TPS film-forming solution treated with

231 HPP was significantly (p < 0.05) lower than that treated with TP. In general, the viscosity of

232 the starch film-forming solutions treated with HPP is lower than that treated with TP, mainly

233 owing to the remaining part of crystalline structures, which prevent melting as amylopectin

234 molecules are stabilized by partially present amylose (Stolt, Oinonen, & Autio, 2000). Song

235 et al. (2017) also reported that the decrease in viscosity of corn starch solutions treated with
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236 HPP compared to TP was attributed to the maintenance of the granular structure of starch

237 after treatment. Similarly, Papathanasiou et al. (2015) and Pei-Ling, Qing, Qun, Xiao-Song,

238 and Ji-Hong (2012) suggested that the viscosity of starch solution gelatinized via heating was

239 higher than that of the solution gelatinized via HPP. Furthermore, it as reported that

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240 rearrangement of starch structure by HPP could be associated with reduction of viscosity (Liu,

241 Wang, Cao, Fan, & Wang, 2016).

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242

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3.5. Optical properties

244 Similar values of L*, a*, and b* were observed for both starch films (Table 4). The

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245 results indicate that BS and TPS films with similar optical properties were obtained, although
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246 different methods were applied to gelatinize the starches. Furthermore, the BS film prepared

247 using HPP had a lower opacity than that prepared using TP, whereas the opposite result was
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248 observed for the TPS films. This difference could be due to the different effects of HPP under

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specific conditions, such as starch type, pressure level, temperature, and treatment time. As

250 A-type starches have more sensitivity to HPP (Shen et al., 2017), the BS is gelatinized more
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251 easily, resulting in high transparency.


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253 3.6. DSC analysis


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254 The onset (To), melting (Tm) temperature, and gelatinization enthalpy (∆H) of BS
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255 and TPS films were analyzed (Fig. 2, Table 5). The HPP treatment increased the values of To,

256 Tm, and ∆H of the BS films compared to TP. Furthermore, To and ∆H of the TPS films

257 prepared using HPP were higher than those of the films prepared using TP, but Tm of the

258 TPS films prepared using HPP was slightly lower than that prepared using TP. These results

259 indicate that higher thermal energy is required to dissociate the interactions of the film matrix

260 using HPP as compared to TP. Furthermore, the films prepared using TP exhibited lower ∆H
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261 values compared to the films prepared using HPP for all the samples. These results might be

262 related to the mechanism of HPP. According to the study by Gutiérrez, Suniaga, Monsalve,

263 and García (2016), low enthalpy (∆H) values are associated with the weakening of

264 interactions in the starch films treated with TP. In general, hydrogen bonds or amylopectin

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265 double-helix of starch can be easily broken at high temperatures (Yang, Chaib, Gu, & Hemar,

266 2017). Contrary to TP, starch films prepared using HPP had a relatively higher percentage of

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267 crystalline structure, and amylopectin double-helix was maintained after treatment

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(Papathanasiou et al., 2015; Stolt et al., 2000), leading to higher ∆H. Therefore, the thermal

269 properties of the starch films were affected by the method of film preparation, and

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270 gelatinization via HPP improved the thermal stability of the films.
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272 3.7. SEM analysis


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273 Fig. 3 illustrates the cross-sectional SEM images of the films. Overall, a compact and

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dense structure was observed for both films regardless of the processing type. However, the

275 cross-section of the TPS films prepared using TP demonstrated slightly rougher morphology
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276 than that of the films prepared using HPP. These results can be explained by the difference in
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277 the MC values of the samples. As water can act as a plasticizer, high moisture content is

278 closely associated with smooth cross-sectional images of the films.


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279
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280 4. Conclusions

281 BS and TPS were used as film base materials. HPP for starch gelatinization was used

282 for the preparation of the films instead of TP, and the results indicate that HPP can improve

283 the physical property, water resistance, and thermal stability of the films compared to the

284 films prepared using TP regardless of the starch type. Therefore, our study suggests that HPP

285 can be used as a cold gelatinization method for the preparation of starch films.
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356 Shen, X., Shang, W., Strappe, P., Chen, L., Li, X., Zhou, Z., & Blanchard, C. (2017).

357 Manipulation of the internal structure of high amylose maize starch by high pressure

358 treatment and its diverse influence on digestion. Food Hydrocolloids.

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359 Song, M. R., Choi, S. H., Oh, S. M., Kim, H. Y., Bae, J. E., Park, C. S., ... & Baik, M. Y.

360 (2017). Characterization of amorphous granular starches prepared by high hydrostatic

361 pressure (HHP). Food Science and Biotechnology, 26(3), 671-678.

362 Song, N. B., Lee, J. H., Al Mijan, M., & Song, K. B. (2014). Development of a chicken

363 feather protein film containing clove oil and its application in smoked salmon packaging.

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368 starch-chitosan bilayer films containing essential oils. Food Hydrocolloids.

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373 starch in excess water. Critical Reviews in Food Science and Nutrition, 54(3), 399-409.
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376 Waterschoot, J., Gomand, S. V., Fierens, E., & Delcour, J. A. (2015). Production, structure,

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382 Yang, Z., Chaib, S., Gu, Q., & Hemar, Y. (2017). Impact of pressure on physicochemical

383 properties of starch dispersions. Food Hydrocolloids, 68, 164-177.

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384 Yang, Z., Gu, Q., & Hemar, Y. (2013). In situ study of maize starch gelatinization under

385 ultra-high hydrostatic pressure using X-ray diffraction. Carbohydrate Polymers, 97(1),

386 235-238.

387 Zhu, F. (2016). Buckwheat starch: structures, properties, and applications. Trends in Food

388 Science and Technology, 49, 121-135.

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390 Figure captions

391 Fig. 1. Water vapor permeability of the BS and TPS films.

392 ■, Thermal processing; □, High hydrostatic pressure.

393

394 Fig. 2. DSC thermograms of the BS and TPS films.

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395

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396 Fig. 3. Cross-sectional SEM images of the starch films.

397 (a) BS film (b) TPS film.s

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398 Magnification: 2000 x.

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400 Table 1
401 Physical properties of the BS and TPS films.

Thickness Tensile strength Elongation


Treatment
(mm) (MPa) at break (%)
BS films TP 0.051 ± 0.003b 13.61 ± 1.06b 5.65 ± 0.23b
HPP 0.063 ± 0.002a 18.29 ± 1.05a 7.92 ± 0.58a

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TPS films TP 0.055 ± 0.001a 24.67 ± 1.03b 5.04 ± 0.56b
HPP 0.055 ± 0.001a 26.92 ± 0.43a 5.71 ± 0.20a
402 Means ± S.D.

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403 Any means in the same column followed by different letters for each starch film are

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404 significantly (p < 0.05) different by Duncan's multiple range test.

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406 Table 2

407 Water solubility and moisture content of the BS and TPS films.

Water solubility Moisture content


Treatment
(%) (%)
BS films TP 19.85 ± 0.33a 12.03 ± 0.51b
HPP 11.67 ± 0.69b 15.76 ± 0.67a

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TPS films TP 28.53 ± 0.68a 12.14 ± 0.45b
HPP 17.53 ± 0.51b 13.40 ± 0.46a

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408 Means ± S.D.
a-b
409 Any means in the same column followed by different letters for each starch film are

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410 significantly (p < 0.05) different by Duncan's multiple range test.

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411 Table 3

412 Viscosity (cP) of the BS and TPS film-forming solutions.

Treatment
Starch
TP HPP
BS 14.80 ± 0.10a 9.40 ± 0.09b

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TPS 451.67 ± 2.08a 11.47 ± 0.21b
413 Means ± S.D.

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414 Any means in the same row followed by different letters are significantly (p < 0.05)

415 different by Duncan's multiple range test.

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416 Table 4

417 Optical properties of the BS and TPS films.

Opacity
Treatment L* a* b*
(A mm-1)
BS films TP 96.91 ± 0.07a -0.31 ± 0.02a 4.14 ± 0.12a 3.63 ± 0.12a
HPP 96.88 ± 0.01a -0.33 ± 0.03a 4.47 ± 0.07a 2.75 ± 0.42b

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TPS films TP 98.33 ± 0.09a -0.14 ± 0.02a 1.74 ± 0.06a 3.92 ± 0.23b
HPP 98.39 ± 0.25a -0.16 ± 0.01a 1.75 ± 0.08a 5.98 ± 0.12a

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418 Means ± S.D.
a-b
419 Any means in the same column followed by different letters for each starch film are

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420 significantly (p < 0.05) different by Duncan's multiple range test.

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421 Table 5

422 Thermal properties of the BS and TPS films.

Treatment To (°C) Tm (°C) ΔH (J/g)

BS films TP 70.52 112.75 78.64


HPP 76.16 120.64 79.30

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TPS films TP 70.92 124.62 56.92
HPP 84.32 122.07 78.40

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Highlights

 Different gelatinization methods have been used for starch films.

 High hydrostatic pressure processing (HPP) and thermal processing were compared.

 HPP treatment improved the physical properties of the starch films.

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 HPP can be used as a method for the preparation of starch films.

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