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Zhang2017 PDF
Zhang2017 PDF
Zhang2017 PDF
a r t i c l e i n f o a b s t r a c t
Article history: Native corn starch slurried in 50% ethanol solution was treated at 60 ◦ C, 70 ◦ C, 80 ◦ C, and 85 ◦ C, respec-
Received 15 February 2017 tively. The resultant starches were investigated by polarized microscopy, scanning electron microscopy
Received in revised form 7 May 2017 (SEM), differential scanning calorimetry (DSC), and X-ray diffractometry (XRD). The Maltese cross of
Accepted 22 May 2017
ethanol-heating treated starch gradually weaken with increasing temperature and completely disap-
Available online 22 May 2017
peared at 85 ◦ C. SEM data indicated the treated granular exhibited a rougher surface with more pores
and grooves than native starch granular, but the shape of the treated starch was still intact. DSC and
Keywords:
XRD data confirmed ethanol-heating treated starch changed from crystalline to non-crystalline struc-
Non-crystalline granular starch
Ethanol-heating treatment
ture at 85 ◦ C. The highest degree of substitution (DS) and corresponding reaction efficiency (RE) for the
Carboxymethyl starch carboxymethylation of native starch were 0.66 and 36.7%, respectively, while the corresponding DS and
RE for non-crystalline granular starches increased by 0.29 and 16.1% at the same reaction condition,
respectively.
© 2017 Elsevier B.V. All rights reserved.
1. Introduction (CH2 COO ) yields starch with many unique properties, such as low
gelatinization temperature, excellent flexibility, improved paste
Starch is the most abundant storage carbohydrate in the bio- storage stability and clarity [15]. Therefore, the CMS is applied
sphere and the main source of energy in human diets [1–3]. It is to wide industry such as thickening of food, drug release, tex-
also a kind of low-costly renewable and biodegradable raw mate- tile sizing, paper coating, and for water-based adhesives [14,16].
rial with distinct physiochemical properties [4,5]. These qualities However, the degree of substitution of CMS was limited due to
account for increasing applications of native starch on various crystallinity of starch, which decreased reaction efficiency of starch
industries for food and non-food utilizations. However, the appli- derivatives. Non-crystalline granular starch, an intermediate state
cation of native starches has been limited in the food industry for between native semi-crystal structure and paste, is a peculiar form
several factors, such as retrogradation, instability of paste under of starch, which shows a granular shape but without crystalline
shearing, acid or freezing, and poor paste clarity et al. [6–8]. There- structure [17]. This new type of starch has many merits, such as, its
fore, most native starches are required to be modified chemically physical and chemical reaction might be accelerated. We suppose
and/or physically to enhance their functional properties and/or that the non-crystalline granular starch may increase the reactiv-
to minimize their defects [9]. Starch derivatives are used in food ity of the starch granules and make the sodium monochloroacetate
products as thickeners, gelling agents, encapsulating agents, in easier to access to the starch granules.
papermaking as wet-end additives for dry strength, surface sizes, Ethanol can be able to complete with starch granular to
and coating binders et al. [10–13]. absorb water, so the granular presents limited swelling and can
Among these starch derivatives, carboxymethyl starch (CMS) obtain granular shape when heating above gelatinization tem-
as a kind of etherified starch has attracted a lot of attention in perature. Therefore, the objective of the present works was to
both research and industry [14]. The presence of functional group prepare non-crystalline granular starch using ethanol-heating
treatment, and resultant starches were investigated by polar-
ized microscopy, scanning electron microscopy (SEM), differential
∗ Corresponding authors.
scanning calorimetry (DSC), and X-ray diffractometry (XRD). Fur-
E-mail addresses: nancyfoodscience@hotmail.com (H. Tao),
hanqchen@hfut.edu.cn (H.-Q. Chen).
http://dx.doi.org/10.1016/j.ijbiomac.2017.05.131
0141-8130/© 2017 Elsevier B.V. All rights reserved.
B. Zhang et al. / International Journal of Biological Macromolecules 103 (2017) 656–662 657
thermore, the CMS was synthesized compared non-crystalline constant rate of 10 ◦ C/min from 30 ◦ C to 100 ◦ C under a continuous
granular starch with native starch. flow of dry N2 gas with an empty pan sealed as a reference.
Fig. 1. The polarized light (Left) and normal light (Right) of native and different temperature treated starches: (A, a) Native starch; (B, b) 60 ◦ C; (C, c) 70 ◦ C; (D, d) 80 ◦ C; (E,
e) 85 ◦ C.
B. Zhang et al. / International Journal of Biological Macromolecules 103 (2017) 656–662 659
swelling of the starch granular [24]. Size distribution of native surface layer was peeled off after ethanol-heating treatment, indi-
and different temperature treated starches was investigated by cating that surface lipids were removed [25]. Swelling of granular
a Malvern Master Sizer 2000 (Fig. 2). The curves of particle size was positively correlated with ethanol-heating treatment temper-
distributions became larger with increasing temperature because ature, but the integrity of the starch granular was still observed
hydration of starch granular (swelling) could be induced by heating. [23]. This phenomenon could be attributed to that ethanol was able
to protect starch granular from swelling while thermal treatment
could destroy crystalline structure of the granular, which was in
3.3. Field emission scanning electron microscopy (FE-SEM)
agreement with the results of light microscopy.
SEM micrographs of native and different temperature treated
starches were shown in Fig. 3. Some morphological modifications 3.4. Differential scanning calorimetry (DSC)
were observed on the surface of the starch granular treated with
different temperature, but these changes did not significantly affect The DSC curves of native and different temperature treated
the shape of the granular. The granular exhibited a rougher surface starches were presented in Fig. 4. The onset (To ) temperature of
with more pores and grooves than the native starch granular. The gelatinization gradually increased with increasing ethanol-heating
660 B. Zhang et al. / International Journal of Biological Macromolecules 103 (2017) 656–662
Fig. 3. SEM micrographs of native and different temperature treated starches: (A) native starch; (B) 60 ◦ C; (C) 70 ◦ C; (D) 80 ◦ C; (E) 85 ◦ C.
treated temperature, which indicated that thermal treatment change could not be determined, which indicated crystalline region
firstly destroyed the weaker crystalline structure of starch gran- was completely destroyed and had been transformed into amor-
ular. The conclusion (Tc ) temperature of gelatinization maintained phous region.
unchanged, suggesting that the strongest crystalline structure of
the starch granular was not influenced. When the temperature was
3.5. X-ray patterns
85 ◦ C, To and Tc were disappeared, which claimed that there was
no crystalline structure in the starch granular. The gelatinization
X-ray diffraction patterns of native and different temperature
enthalpy change also decreased with the increase of tempera-
treated starches were shown in Fig. 5. Native corn starch with a
ture. When the temperature was 85 ◦ C, the gelatinization enthalpy
typical A-type crystalline polymorphic structure was characterized
B. Zhang et al. / International Journal of Biological Macromolecules 103 (2017) 656–662 661
Native starch
o
60 C
o
70 C
o
80 C
o
85 C
40 60 80 100
Fig. 5. X-ray diffraction patterns of native and different temperature treated
o
Temperature ( C) starches.
100
1.0 Nonocrystalline granular starch
Native starch Nonocrystalline granular starch
Native starch
0.8 80
RE (%)
0.6
60
DS
0.4
40
0.2
0.0 20
0 1 2 0 1 2
nSMCA/nAGU nSMCA/nAGU
Fig. 6. The effect of the molar ratio of sodium monochloroacetate to anhydroglucose unit on the degree of substitution (DS) and the reaction efficiency (RE) for the
carboxymethylation of native and non-crystalline granular starches.
662 B. Zhang et al. / International Journal of Biological Macromolecules 103 (2017) 656–662
were 0.95 and 52.8%, respectively. However, the corresponding [10] T. Heinze, A. Koschella, Macromol. Symp. 223 (2005) 13–39.
DS and RE for native starch were 0.66 and 36.7% at the same [11] J.M. Fang, P.A. Fowler, J. Tomkinson, C.A.S. Hill, Carbohydr. Polym. 47 (2002)
245–252.
molar ratio of sodium monochloroacetate to anhydroglucose unit, [12] M.C. Sweedman, M.J. Tizzotti, C. Schäfer, R.G. Gilbert, Carbohydr. Polym. 92
respectively. These results indicated that the non-crystallization (2013) 905–920.
process of native starch was beneficial to synthesize CMS. This [13] B. Zhang, Y. Pan, H. Chen, T. Liu, H. Tao, Y. Tian, Food Chem. 214 (2017)
213–217.
non-crystalline granular starch was seen as a new raw material [14] O.S. Lawal, M.D. Lechner, B. Hartmann, W.-M. Kulicke, Starch - Stärke 59
to prepare various modified starch and products. (2007) 224–233.
[15] H. Qiu, L. He, Polym. Adv. Technol. 10 (1999) 468–472.
[16] D. Bhattacharyya, P.N. Chhaya, R.S. Singhal, P.R. Kulkarni, Lipid/Fett 97 (1995)
Acknowledgements 432–434.
[17] P. Liu, B. Zhang, Q. Shen, X. Hu, W. Li, Int. J. Food Eng. 6 (2010).
This study was financially supported by the Natural Science [18] B. Zhang, S. Dhital, E. Haque, M.J. Gidley, Carbohydr. Polym. 90 (2012)
1587–1594.
Foundation of Anhui Province (No. 1708085QC78) and National
[19] B. Zhang, C. Wu, H. Li, X. Hu, Z. Jin, Y. Tian, X. Xu, Starch-Stärke 67 (2015)
Natural Science Foundation of China (No. 31601429). 577–584.
[20] J. Liu, J. Ming, W. Li, G. Zhao, Food Chem. 133 (2012) 1196–1205.
[21] S. Li, R. Ward, Q. Gao, Food Hydrocolloids 25 (2011) 1702–1709.
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