Food Research International 41 (2008) 579585

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Food Research International

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In vitro starch digestibility and estimated glycemic index of chemically modied corn starches
Hyun-Jung Chung a, Dong-Hoon Shin b, Seung-Taik Lim c,*
a

Guelph Food Research Centre, Agriculture and Agri-Food Canada, 93 Stone Road West, Guelph, ON, Canada N1G 5C9 Department of Food and Biotechnology, Korea University, Seoul 136-701, Republic of Korea c School of Life Sciences and Biotechnology, Korea University, Seoul 136-701, Republic of Korea
b

a r t i c l e

i n f o

a b s t r a c t
Normal corn starch was chemically modied by oxidation, acetylation, hydroxypropylation, and crosslinking, and the digestibility and glycemic indices (GI) of these modied starches were examined by in vitro hydrolysis using pancreatic a-amylase. During the early stage of hydrolysis (up to 60 min) with prime (ungelatinized) starches, the modied starches were hydrolyzed at greater extents than the unmodied starches. However, at the late stage of hydrolysis (after 3 h), the modied starches showed lower degrees of hydrolysis than the unmodied starch. The amount of resistant starch (RS) in prime starches were 23.4%, 35.1%, 34.2%, and 13.9% in the acetylated, oxidized, hydroxypropylated, and cross-linked starches, respectively, whereas the unmodied starch contained 11.9%. The amount of slowly digestible starch (SDS) was decreased as the RS content was increased by the modication, indicating that some of the SDS transformed to RS. By gelatinization, all the starches, regardless of type of modication, were more quickly hydrolyzed and reached maximum levels within 20 min. Like the prime starches, the modied starches contained higher contents of undigested starches after gelatinization. The modications except cross-linking reduced rapidly digestible starch (RDS) content but increased the RS content when the starches were gelatinized. The hydroxypropylated starch had the lowest GI values, which were estimated from the hydrolysis proles (70.6 and 86.2 in prime and gelatinized states, respectively), whereas the GI values of cross-linked starch were similar to those of the unmodied starch. Therefore, chemical substitution such as hydroxypropylation and acetylation, and oxidation can be used to reduce the starch digestibility and raise the RS content. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 14 January 2008 Accepted 23 April 2008

Keywords: Starch digestibility Estimated glycemic index Modied starch

1. Introduction Current dietary guidelines focus on lowering dietary fat and increasing complex carbohydrate intake, such as starch and dietary ber (Roberts, 2000). Starch contributes as much as 7080% of the total carbohydrates in normal diets. For nutritional purposes, starches are classied on the basis of their rate and extent of digestion into three categories: rapidly digestible starch (RDS), slowly digestible (SDS), and resistant starch (RS) (Englyst, Kingman, & Cummings, 1992). RDS is the starch fraction that causes a rapid increase in blood glucose level after ingestion. SDS is the starch fraction that is digested slowly but completely in the human small intestine. RS is the starch portion that cannot be digested in the small intestine, but may be fermented in the large intestine (Englyst et al., 1992). The potential health benets of SDS include stable glucose metabolism, diabetes

* Corresponding author. Tel.: +82 2 3290 3435; fax: +82 2 927 5201. E-mail address: limst@korea.ac.kr (S.-T. Lim). 0963-9969/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodres.2008.04.006

management, mental performance, and satiety (Lehmann & Robin, 2007). The health benets of RS have been reported as prevention of colon cancer, hypoglycemic effects, substrate for the growth of the probiotics, reduction of gall stone formation, hypocholesterolemic effects, inhibition of fat accumulation, and increasing absorption of minerals (Sajilata, Singhal, & Kulkarni, 2006). The glycemic index (GI) characterizes the carbohydrates consumed in different types of foods on the basis of postprandial level of blood glucose (Jenkins, 2007; Jenkins et al., 1982). Long-term intake of low GI foods was reported to associate with the reduced incidence and prevalence of heart disease, diabetes, and also some forms of cancer (Brand-Miller, 2007; Jenkins, 2007; Roberts, 2000; Wolever & Mehling, 2002). Starch itself is often used as a food ingredient to improve physical properties of the host foods, and to overcome undesirable changes during processing or storage. Prior to its use, starch can be structurally modied by various chemical means to enhance its functions as ingredient (Eliasson & Gudmundsson, 1996). The overall effects of the chemically modied starches

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have been thoroughly evaluated, and the degree of chemical modications and the use of the modied starches are legally regulated (CFR, 2006). It has been reported that structural modication of starch may change its digestibility. Hoover and Sosulski (1985) reported the in vitro digestibility of acetylated legume starch (degree of substitution 0.05) with porcine pancreatic a-amylase for 6 h was reduced by up to 10%, as compared to native starch. The reduced degree of hydrolysis was suggested to be due to the steric hindrance imposed by the bulky substituents and the electron withdrawing effect of the carbonyl oxygen of the acetyl groups. Raben, Andersen, Karberg, Holst, and Astrup (1997) also reported that an acetylated potato starch improved the glycemic, insulinemic and satiating properties in a meal from an in vivo test because the acetylation decreased the susceptibility of starch to a-amylase. Hydroxypropylation was also found to inuence the susceptibility of starch to digestive enzymes (Hoover, Hannouz, & Sosulski, 1988; Wootton & Chaudhry, 1981). The in vitro digestibility of hydroxypropylated wheat starch was reduced as the degree of substitution (DS) increased, indicating that the enzymatic attack was restricted by substituting groups (Wootton & Chaudhry, 1981). Similarly, the digestibility of a hydroxypropylated eld pea starch was decreased with increases in the molar substitution (MS) up to the levels of 0.08 (Hoover et al., 1988). However, further increases in MS levels (>0.08) caused an increased digestibility presumably due to the increased swelling. Studies examining the in vitro digestion of cross-linked starches have yielded contradictory observations. Some researchers have reported that the cross-linking with phosphorylation may reduce the rate of digestion (Wepner, Berghoper, Miesenberger, Tiefenbacher, & Na, 1999; Woo & Seib, 2002), whereas others have not observed any change (Hoover & Sosulski, 1986). The discrepancy may reect that there were differences in the type and degree of cross-linking. Bjrck and colleagues systemically studied the digestibility of native and chemically modied potato starches (cross-linked by distarch phosphate, acetylated and hydroxypropylated starches) by in vitro and in vivo tests (Bjrck, Gunnarsson, & stergrd, 1989; stergrd, Bjrck, & Gunnarsson, 1988). From the in vitro test, when these modied starches were in a granular (ungelatinized) state, cross-linking or acetylation did not affect the digestibility. Etherication with hydroxypropyl groups, however, increased the amylolysis because the enzymes had better access to starch because the hydroxypropylation helped the starch granules to swell. When the starch was gelatinized, the digestibility of starch was reduced by the hydroxypropyl groups. In contrast, cross-linking with phosphate esters only had minor effects on the digestibility of the gelatinized starch (stergrd et al., 1988). In the in vivo tests with rats, the cross-linking or acetylation did not appreciably affect the digestibility of potato starch, whereas the etherication with hydroxypropyl groups signicantly reduced its digestion and absorption (Bjrck et al., 1989). Although the digestibility of chemically modied starch has been studied by many researchers, the nutritional fractions of starch (RDS, SDS, and RS) have not been discussed. In addition, the effects of the chemical modications on the digestion behavior, in native and gelatinized states of starch, are not fully understood. The purpose of this study was to investigate the in vitro digestibility of chemically modied corn starches (acetylated, oxidized, hydroxypropylated, and cross-linked starches) at the modication levels that are commercially permissible for food uses. Not only the ungelatinized prime starches but the gelatinized starches were tested for comparison. From the digestion prole, various starch fractions of different digestion rates were determined and glycemic indices were estimated.

2. Materials and methods 2.1. Materials Normal corn starch was provided by Samyang Genex Company (Seoul, Korea). Acetic anhydride, propylene oxide, and sodium hypochlorite were purchased from Junsei Chemical Co. (Tokyo, Japan). Sodium trimetaphosphate (STMP), sodium tripolyphosphate (STPP), and sodium sulfate were purchased from Sigma Aldrich Company (St. Louis, MO). 2.2. Preparation of starch samples The modied starches were prepared within the ranges that are commercially permissible for food-grade products (CFR, 2006). The corn starch slurry was prepared by dispersing the starch in distilled water. For acetylation, acetic anhydride (6 g, 6% of solid) was added dropwise to the slurry (100 g starch, 35% w/v) with simultaneously stirring at room temperature while maintaining pH within a range 8.08.4. The reaction was allowed to proceed for additional 5 min after completion of acetic anhydride addition. For oxidation, sodium hypochlorite solution (6 g, 0.48 g active chlorine/100 g) was slowly added to the starch slurry (100 g starch, 35% w/v) and the mixture was stirred for 30 min at 35 C while maintaining the pH at 9.5 0.1. Hydroxypropylated starch was prepared by injecting propylene oxide (10 ml) into the starch slurry (100 g starch in 150 ml water) that had been adjusted to pH 11.5, and stirred in a water bath at 40 C for 40 h. Cross-linked starch was prepared by adding the mixture of STMP and STPP (99/1% w/w, 4 g) in the starch slurry (100 g starch in 140 ml water) that had been adjusted to pH 11, and stirred for 3 h at 45 C. All the starch slurries, which were treated differently, were neutralized by adding 1N HCl, washed with distilled water three times (300 ml each time) and then dried at 40 C overnight in a convection oven. Acetyl, carbonyl, hydroxypropyl, and phosphorous contents in the starch products were determined by following the methods of Wurzburg (1964), Wang and Wang (2003), Johnson (1969), and Smith and Caruso (1964), respectively. 2.3. Paste viscosity and swelling volume The paste viscosities of the modied starches were determined by using a Rapid Visco Analyzer (RVA) (Newport Scientic Inst., Warriewood, Australia). The starch slurry (7.0% w/w, dsb) was heated from 50 to 95 C for 3.5 min, held at 95 C for 5 min, cooled down to 50 C for 3.5 min and then held at 50 C for 4 min. The swelling volume was determined by using the method of Crosbie (1991) with a modication. The dried starch samples (0.5 g) were placed in a falcon tube (15 ml), distilled water (10 ml) was added slowly, and the tube was kept at room temperature for 20 h. The swelling volume was calculated by dividing the total volume of the swollen starch by the original dry weight of the initial starch. 2.4. In vitro starch digestibility The in vitro starch digestibility was determined by following the method of Englyst et al. (1992) as modied by Chung, Lim, and Lim (2006). The amount of starch fractions based on digestibility was calculated by using the method of Englyst et al. (1992) with minor modication due to the slow digestion of prime (ungelatinized) starch. The rapidly digestible starch (RDS) was dened as the starch fraction that was hydrolyzed within 20 min incubation and resistant starch (RS) was dened as the fraction that remained unhydrolyzed after 180 min incubation. The slowly digestible

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starch (SDS) content was calculated as the difference between RDS and RS. 2.5. Estimation of glycemic index (GI) The hydrolysis index (HI) was calculated on the basis of the starch hydrolysis curve (0180 min) as the percentage of total glucose released over 180 min in comparison to that released from white bread over the same duration (Granfeldt, Bjrck, Drews, & Tovar, 1992). The glycemic index (GI) was then estimated by using the following equation of Goni, Garcia-Alonso, and Saura-Calixto (1997): GI = 39.71 + 0.549HI. 2.6. Statistical analyses All analyses were performed at least in triplicates. Statistical analyses were carried out with Duncans multiple test (P < 0.05) using statistical software SPSS V. 8.2 (SPSS Institute Inc., Cary, NC). 3. Results and discussion 3.1. Characterization of modied starch The acetyl, carbonyl, hydroxypropyl, and phosphorus contents in the acetylated, oxidized, and hydroxypropylated, and crosslinked starches tested were 0.475%, 0.482%, 2.086%, and 0.137%, respectively. Based on these results, the hydroxypropylated starch showed the highest degree of modication among the starch samples. The swelling volume of starch, however, was the highest for the acetylated starch (5.5 ml/g) and lowest for the cross-linked starch (2.9 ml/g). The hydroxypropylated, oxidized, and unmodied starches showed intermediate swelling volumes between the acetylated and cross-linked starches (3.9, 3.1, and 3.0 ml/g, respectively). In the viscosity prole during pasting, the hydroxypropylated (HP) and acetylated starches (AC) exhibited increased paste viscosities and decreased pasting temperatures compared to the unmodied starch (UM). The cross-linked starch (CL) and oxidized starch (OX) did not show any viscosity in the prole (Fig. 1). The level of cross-linking was too high for the starch to swell and gela-

tinize, and the oxidation caused the starch chain degradation so that the pasting viscosity was too low (Tran, Piyachomkwan, & Sriroth, 2007; Veelaert, de Wit, Gotlieb, & Verhe, 1997). The changes in the pasting behavior appeared the most signicant by the hydroxypropylation, possibly due to the higher level of modication compared to the other starches. 3.2. Enzymatic hydrolysis The digestion behavior of the prime (granular) starches depended on the type of modication (Fig. 2). During the early stage of the hydrolysis (up to 60 min), the oxidized starch (PCL) showed the most rapid hydrolysis of all the starches. This is due to the starch degradation occurred by the oxidation as revealed by its viscogram (Fig. 1), which enhanced the accessibility of the starch chains to the enzyme. The hydroxypropylated starch (PHP) also showed an increased rate of hydrolysis during the early stage as compared to the unmodied starch. However, the acetylated (PAC) and cross-linked (PCL) starches did not differ from the unmodied starch (PUM) in terms of the early hydrolysis rate. After 60 min, the degree of hydrolysis became substantially different among the starches tested (Fig. 2). In the late stage of hydrolysis (after 3 h), the unmodied starch (PUM) showed higher level of hydrolysis than did the modied starches. The extent of hydrolysis after 3 h in PAC, PHP, and POX were 74.0%, 67.6%, and 69.9%, whereas that of the unmodied starch (PUM) and cross-linked starch (PCL) were 83.7% and 81.9%, respectively. Studies examining the in vitro digestion of chemically modied starches in granular state have yielded contradictory observations. stergrd et al. (1988) and Wootton and Chaudhry (1981) reported that hydroxypropylation increased the enzymatic hydrolysis extent during a treatment by porcine a-amylase for 60 min due to the opening of the starch granule which had been caused by the modication. However, Hoover et al. (1988) observed that the digestibility of eld pea starch was decreased by hydroxypropylation (MS below 0.08). Liu, Ramsden, and Corke (1997) showed that the acetylation with normal, waxy and high amylose maize starches caused increase in digestibility by a-amylase (14 h). However, Hoover and Sosulski (1985) reported the in vitro digestibility

2000

100

1500

1000

70

60 500 50

CL ,OX
0

40 0 2 4 6 8 10 12 14

Time (min)
Fig. 1. RVA pasting viscograms of chemically modied corn starches. UN, unmodied starch; AC, acetylated starch; OX, oxidized starch; HP, hydroxypropylated starch; and CL, cross-linked starch.

Temperature (C)

Viscosity (cP)

UM AC OX HP CL

90

80

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80

Total starch hydrolysis (%)

60

40 PUM PAC POX PHP PCL

20

0 0 50 100 150 200

Time (min)
Fig. 2. Starch hydrolysis patterns of the chemically modied corn starches in the prime (granular) state with porcine pancreatic a-amylase for 3 h at 37 C. PUM, unmodied starch in the prime state; AC, acetylated starch; OX, oxidized starch; HP, hydroxypropylated starch; and CL, cross-linked starch.

of legume starch decreased after acetylation (degree of substitution (DS) 0.05) after 6 h incubation with porcine pancreatic a-amylase. These discrepancies may reect the differences in degree of substitution and digestion analysis procedure. It was postulated from our result that the enzyme susceptibility of the substituted starches in granular state was increased only during the early stage of the hydrolysis (up to 60 min) because of the increased level of swelling by the substituting groups. The enzyme accessed more readily when starch was more swollen. However, the substituted groups were inert to the enzymatic action, and thus provided the granular starch the resistance to enzymatic hydrolysis. Thus the maximum level of hydrolysis at the late stage of digestion (after 3 h) was decreased by the modications. The cross-linked starch (PCL) showed a slightly decreased level of hydrolysis after 3 h as compared to the unmodied starch (PUM) (81.9% vs. 83.7%). Similar result was reported by Hoover and Sosulski (1986) with legume starches and by stergrd et al. (1988) with potato starch. Cross-linking is currently used to prepare commercial resistant starches (Type IV). Woo and Seib (2002) reported that cross-linking of starch with a mixture of STMP and STPP produced a resistant starch against amylase digestion, and the inhibition against the enzymatic attack increased with the degree of cross-linking. Compared to the cross-linked starch reported by Woo and Seib (2002), the cross-linked starch tested here was treated at a much less degree of reaction (0.137% P). Consequently, the enzymatic hydrolysis pattern of the cross-linked starch was similar to that of the unmodied starch although the starch was resistant to pasting (Fig. 1). The hydrolysis by the pancreatic a-amylase was considerably enhanced by gelatinization (Fig. 3). With the rapid hydrolysis glucose was released fast, and the hydrolysis level reached plateaus within 20 min (small gure in Fig. 2). However, the maximum level of hydrolysis was different among the starches tested. The unmodied starch (GUM) and cross-linked starch (GCL) were hydrolyzed up to 93%. The substituted starches (GHP and GAC, 80.0% and 85.8%, respectively) and the oxidized starch (GOX, 87.2%), however, displayed substantially lower values for the maximum hydrolysis than that of the unmodied starch. As with the prime (granular) starches, the substitution and oxidation also inhibited the enzymatic reaction of the gelatinized starches.

Hoover et al. (1988) and Wootton and Chaudhry (1981) observed that hydroxypropylation decreased the enzyme susceptibility of pea and wheat starches even after the starches were pasted. stergrd et al. (1988) also found that the substitution with acetyl or hydroxypropyl groups reduced the enzyme susceptibility in the gelatinized starches. They also suggested that the hydroxypropyl groups had greater effect than the acetyl groups on the enzyme resistance because more bulky hydroxypropyl group provides a greater hindrance to attack by enzyme than the acetyl group (Hoover & Sosulski, 1986; Wootton & Chaudhry, 1981). It has been also suggested that the presence of bulky substituents on C2 of the glucose unit would sterically hinder the proper positioning of the substrate into the active site of a-amylase and also effectively restrict enzyme attack on adjacent glycosidic bonds of unsubstituted glucose residues (Hoover & Sosulski, 1986; Hoover & Zhou, 2003; stergrd et al., 1988). In the present study, the results observed with the gelatinized starches were similar to those reported in the previous literatures. Consequently, it is clear from the results that substitution or oxidation, in prime or in gelatinized states, reduces the ultimate level of enzymatic hydrolysis of starch, whereas the early digestion of granular starch increases due to the enhanced swelling of starch granules. For the comparison among the modications used for food starches, more experiments with different types and degrees of modications should be done. 3.3. Starch fractions of different digestibility The rapidly and slowly digestible starches (RDS and SDS), and resistant starch (RS) of the modied corn starches in the prime and gelatinized states were measured based on the enzymic hydrolysis patterns (Table 1). In the prime state, the oxidized starch (POX) had the highest amount of RDS (33.5%) among the starches tested, followed by the hydroxypropylated starch (PHP, 27.9%). Both starches had slightly higher RDS contents than that of the unmodied starch (25.6%). The cross-linked (PCL, 24.0%) and acetylated starches (PAC, 24.1%), however, showed slightly lower RDS contents than that of the unmodied starch. As shown in the hydrolysis curve (Fig. 2), the oxidized starch was rapidly hydrolyzed during the early stage of digestion (up to 60 min) because the chain degradation of starch occurred during the oxidation,

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100

80

Total starch hydrolysis (%)

60

90

40
80

20
70 0 10 20 30

GUM GAC GOX GHP GCL

0 0 50 100 150 200

Time (min)
Fig. 3. Starch hydrolysis patterns of the chemically modied corn starches in the gelatinized state after heating in boiling water bath for 20 min prior to treatment with porcine pancreatic a-amylase for 3 h at 37 C. GUM, unmodied starch in the gelatinized state; AC, acetylated starch; OX, oxidized starch; HP, hydroxypropylated starch; and CL, cross-linked starch.

Table 1 Amount of rapidly and slowly digestible starches (RDS and SDS), and resistant starch (RS) of native and modied corn starchesA Starches PUMB PAC POX PHP PCL GUM GAC GOX GHP GCL
A

RDS (%) 25.6 0.1g 24.1 0.3h 33.5 0.4e 27.9 0.3f 24.0 0.2h 92.7 0.2a 85.7 0.1c 87.0 0.1b 80.4 0.2d 93.0 0.1a

SDS (%) 62.8 0.3a 52.5 1.4b 31.4 0.7d 37.9 0.1c 62.1 0.8a 0.01 0.00f 0.00 0.00f 0.00 0.00f 0.05 0.01e 0.02 0.01f

RS (%) 11.7 0.3g 23.4 1.1c 35.1 0.5a 34.2 0.3b 13.9 0.7e 7.3 0.2h 14.3 0.1e 13.0 0.1f 19.5 0.3d 7.0 0.1h

Values followed by a different superscript in each column are signicantly different (P < 0.05). B PUM, unmodied starch in the prime (granular) state; GUM, unmodied starch in the gelatinized state; AC, acetylated starch; OX, oxidized starch; HP, hydroxypropylated starch; and CL, cross-linked starch.

which was evidenced in the viscogram (Fig. 1). Thus, the fast rate of hydrolysis was expected to result in the greatest amount of RDS. The hydroxypropylated starch (PHP) had an exceptionally greater ability of swelling than other starches tested as evidenced in viscogram (Fig. 1). The swelling of the starch granules is likely to enhance the access of digestive enzyme inside the granules and thus increase the RDS content. The acetylated starch (PAC) swelled more readily than did the unmodied starch. However, the RDS content in PAC was less than that in the unmodied starch. This may indicate that the acetyl groups could hinder the enzymatic action even during the early stage of hydrolysis (up to 60 min). The SDS content of the unmodied starch (PUM) was 62.8%, which was similar to that of the cross-linked starch (PCL, 62.1%) (Table 1). The oxidized or substituted starches, however, contained signicantly less amounts of SDS than did the unmodied starch. On the other hand, the RS content was elevated by the modications. For instance, the RS contents of oxidized (POX) and hydroxypropylated starches (PHP) were 35.1% and 34.2%, respectively,

whereas that of unmodied starch (PUM) was 11.7%. The increase in RS and decrease in SDS by the modications suggested that the SDS may be partially transformed to RS by the modications. However, it was not possible to directly compare the effect of the type of substituent on the resistance to the enzymatic digestion, because the degrees of modication differed for the starches tested. It has been reported that the gelatinized starch hydrolyzes more readily than does its prime type (Chung et al., 2006). This is consistent with the hydrolysis curves observed (Fig. 2 vs. Fig. 3). Regardless of modication, the gelatinized starches tested had higher RDS contents and lower SDS and RS contents than did the prime starches. In their gelatinized states, the cross-linked starch (GCL) had similar RDS (93.0%) and RS contents (7.0%) as those of the unmodied starch (92.7% and 7.3%, respectively). Han and BeMiller (2007), however, reported that cross-linking of waxy corn starch with POCl3 (0.16% w/w) produced a decrease in RDS content but an increase in RS content. The differences in the conditions and degree for the reaction might result in different digestion behaviors. The RDS content of substituted (GAC, 85.7% and GHP, 80.4%) or oxidized (GOX, 87.0%) starches had much lower than that of unmodied (GUM, 92.7%) or cross-linked (GCL, 93.0%) starches (Table 1). The SDS contents of the gelatinized starches exhibited nearly 0% due to the rapid enzymatic action on the gelatinized starch. The substituted or oxidized starches contained much higher amount of RS compared to the unmodied or cross-linked starches. In particular, the hydroxypropylated starch (GHP) contained 19.5% of RS, which was more than double RS content of the unmodied starch (GUM, 7.3%). These observations suggested that chemical substitution and oxidation generate resistant starch in both prime and gelatinized states. In granular prime starch, RS formation appeared by the transformation mainly from slowly digestible starch, whereas it was by the transformation mainly from rapidly digestible starch in gelatinized starch. 3.4. Hydrolysis kinetics and estimated glycemic index The in vitro digestion results including equilibrium concentrations (C1), kinetic constants (k), hydrolysis index (HI), and

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Table 2 Equilibrium concentration (C1), kinetic constant (k), hydrolysis index (HI) and estimated glycemic index (GI) for native and modied corn starchesA Starches PUM PAC POX PHP PCL
B

C 1 (%) 88.3 0.3 76.6 1.1f 65.8 0.5g 64.9 0.3h 86.1 0.7d 92.7 0.2a 85.7 0.1d 87.0 0.1c 80.5 0.3e 93.0 0.1a
b

kC 0.017 0.000 0.019 0.001f 0.036 0.001d 0.028 0.000e 0.016 0.000g 0.302 0.019b 0.387 0.035a 0.387 0.038a 0.241 0.015c 0.334 0.030b
g

HI 64.8 0.1 58.3 0.3g 58.6 0.3g 56.0 0.4h 62.1 0.2f 98.0 0.2a 90.6 0.1c 92.0 0.1b 85.0 0.3d 98.2 0.1a
e

GID 75.3 0.0e 71.7 0.1g 71.9 0.2g 70.5 0.2h 73.8 0.1f 93.5 0.1a 89.5 0.1c 90.2 0.1b 86.4 0.1d 93.6 0.1a

the digestibility of gelatinized potato starch in rat was not affected by cross-linking and acetylation whereas hydroxypropylation signicantly reduced the extent of digestion by about 50%. Consequently, the glycemic index, which represents the overall contribution in increasing the blood glucose level, could be decreased by chemical substitution and oxidation, but the cross-linking with phosphate had only minor effects. 4. Conclusions Both the in vitro digestibility and estimated glycemic index of starch could be changed by the chemical modications which are currently practiced for the preparation of food starches, such as oxidation, acetylation, hydroxypropylation, and cross-linking. While cross-linking induced substantial changes in pasting characteristics of starch, it did not affect starch digestibility as much as oxidation or substitutions. The substitution (hydroxypropylation and acetylation) and oxidation contribute in raising the amount of resistant starch (RS) content by decreasing SDS content in prime starch, and decreasing RDS content in gelatinized starch. Hydroxypropylation appeared more effective in hindering enzymatic digestion than oxidation and acetylation, within the reaction ranges allowed for food starches. Thus the hydroxypropylated starch showed the lowest value of glycemic index (GI) among the starch samples tested. The chemical modications thus not only improve the physical properties but also control the digestibility of starch. References
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GUM GAC GOX GHP GCL

A

Values followed by a different superscript in each column are signicantly different (P < 0.05). B PUM, unmodied starch in the prime (granular) state; GUM, unmodied starch in the gelatinized state; AC, acetylated starch; OX, oxidized starch; HP, hydroxypropylated starch; and CL, cross-linked starch. C C1 and k were determined by the equation, C = C1(1 ekt). D GI was calculated from equation proposed by Goni et al. (1997).

estimated glycemic index (GI) are listed in Table 2. The equilibrium concentrations (C1), the hydrolysis extent when the hydrolysis curve reached a plateau, ranged from 65% to 88% in the prime state, and from 80% to 93% in the gelatinized state (Table 2). The C1 values of oxidized starch (POX, 64.9%) and hydroxypropylated starch (PHP, 65.8%) were lower by more than 20% than those of the unmodied (88.3%) and cross-linked (86.1%) starches. In gelatinized starch, the hydroxypropylated starch (GHP, 80.5%) had the lowest C1 value among the tested sample, whereas the C1 value of cross-linked starch (GCL, 93.0%) was similar to that of the unmodied starch (GUM, 92.7%). The kinetic constants (k), which reected the rate of hydrolysis, were signicantly higher in the gelatinized starches than the prime starches. It indicates that the gelatinized starches are much susceptible to the digestive enzymes and much rapidly hydrolyzed than the granular starches. The oxidized starch (POX, 0.036) in prime state had the highest k value, followed by the hydroxypropylated starch (PHP, 0.028), whereas the unmodied (PUM, 0.017) and cross-linked starches (PCL, 0.016) had relatively lower k values. These differences in k values might be due to the rate of enzyme attack by the different degrees of swelling. When starches were gelatinized, the hydroxypropylated starch (GHP) had the lowest k value (0.241), which indicates that the hydroxypropyl substituent effectively hindered the enzyme attack and thus decreased the rate of hydrolysis. From the result of C1 and k values, the hydroxypropylation used in this study was the most effective in hindering the in vitro hydrolysis of starch among the modied starches tested, both in prime and in gelatinized states. The hydrolysis index (HI), another parameter related to digestibility, is used for the estimation of the glycemic index (GI). The HI of the starch samples ranged between 56 and 65 in the prime state, and between 85 and 98 in the gelatinized state (Table 2). The estimated glycemic index (GI) based on the HI ranged between 70.5 and 75.3 and between 86.4 and 93.6, respectively. Among the modications tested, the hydroxypropylation yielded the lowest GI value in both prime and gelatinized states (Table 2). For the crosslinked starch, the GI in prime state was slightly lower than that of the unmodied starch, but similar when both starches were gelatinized. The GI values of the oxidized and acetylated starches appeared between the values of hydroxypropylated and unmodied starches in both prime and gelatinized state. Bjrck et al. (1989) calculated the digestibility of modied starches from a direct measurement of starch in feed and faces with normal rats. They reported the results similar to those in this study, in which

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