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RESEARCH ARTICLEImpact of acid and heat –moisture treatment combination on physicochemical characteristics and resistant starch contents of sweet potato and yam starches Pham Van Hung1,

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RESEARCH ARTICLE

Impact of acid and heat –moisture treatment combination on

physicochemical characteristics and resistant starch contents

of sweet potato and yam starches

Pham Van Hung1, Nguyen Thi Huyen My1and Nguyen Thi Lan Phi2

1

School of Biotechnology, International University, Vietnam National University in HoChiMinh City, HoChiMinh City, Vietnam 2

Faculty of Chemical Engineering, HoChiMinh City University of Technology, HoChiMinh City, Vietnam

The objective of this study is to investigate formation of slowly digestible starch (SDS) and

resistant starch (RS) and change in physicochemical properties of sweet potato and yam

starches under a combination of acid and heat–moisture treatments using three mild

organic acids including acetic acid, lactic acid and citric acid and heating temperature at

110°C for 8 h The results show that the SDS and RS in sweet potato starch significantly

increased from 6.6 and 14.7% in native starch to 8.7–13.2% and 37.5–42.1% in acid and

heat–moisture treated starches, respectively Likewise, the SDS and RS in yam starch

increased from 4.7 and 21.6% in native starch to 10.0–11.3% and 39.0–46.4% in the treated

starches, respectively The RS content in the acid and heat–moisture treated starches was

also significantly higher than that of the heat–moisture treated starches without acid

hydrolysis Yam starch produced higher amount of RS under acid and heat–moisture

treatment as compared to sweet potato starch at the same condition Swelling power and

viscosity of starches significantly decreased, whereas the solubility significantly increased

after treatments The citric acid had the most impact on RS formation and starch properties,

followed by lactic acid and acetic acid As a result, the combination of acid and heat–moisture

treatment is a useful method to produce higher amount of resistant starch, which can be

applied for functional foods

Received: May 29, 2014 Revised: July 8, 2014 Accepted: July 14, 2014

Keywords:

Acid hydrolysis / Heat–moisture treatment / Resistant starch / Sweet potato / Yam

1 Introduction

Starch, the most abundant reserve carbohydrate of many

plants, is also a major component of many food products

Starch in foods after consumption can be classified into

three types based on their digestibility: a rapidly digestible

starch (RDS), slowly digestible starch (SDS) and resistant

starch (RS) [1] RDS and SDS are completely digested and absorbed in the human small intestine that cause the increase in blood glucose level, whereas RS escapes digestion in small intestine and does not contribute to the blood glucose level of healthy individuals Recently, the SDS and RS have received much attention for both its potential health benefits and functional properties The SDS are known to have potential health benefits in a stable glucose metabolism, diabetes management, mental perfor-mance, and satiety [2] The SDS may be used by athletes to provide a longer-lasting source of systemic glucose [3, 4] Although RS is not digested, it is fermented in the large intestine by human microflora to produce short-chain fatty acids The potential health benefits of RS have been reported

as prevention of colon cancer, hypoglycemic effects, substrate for growth of the probiotic microorganisms,

Correspondence: Dr Pham Van Hung, School of Biotechnology,

International University, Vietnam National University, Quarter 6,

Linh Trung Ward, Thu Duc District, HoChiMinh City, Vietnam

E-mail: pvhung@hcmiu.edu.vn

Fax: þ84-8-37244271

Abbreviations: HMT, heat –moisture treatment; RDS, rapidly

digestible starch; RS, resistant starch; SDS, slowly digestible

starch; SPS, sweet potato starch; YS, yam starch

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reduction of gall stone formation, hypocholesterolemic

effects, inhibition of fat accumulation, and increased

absorption of minerals [5] Therefore, the recent studies

focus on production of high amounts of RS from various

starch sources and application of RS as a“low-carbohydrate”

ingredient in food formulations [3]

SDS and RS can be produced by various modification

techniques including physical, chemical, and enzymatic

modifications Heat–moisture treatment (MHT) is a

well-known hydrothermal method to increase the levels of SDS

and RS in starches without destroying their granular

structure [6] In HMT, starch granules are treated at low

moisture levels (<35% moisture, w/w) for a certain time

period (15 min–16 h) and at high temperatures (84–

120°C) [7] Chung et al [8] reported that the RDS decreased

by 10.2, 14.0, and 15.1%, the SDS content increased by 2.5,

2.8, and 4.7%, and the RS content increased by 7.7, 11.2, and

10.4% for corn, pea, and lentil starches, respectively, when

these starches were heat–moisture treated at 120°C as

compared to native starches The SDS contents of maize,

potato, cocoyam, yam, plantain, rice, and sweet potato under

hydrothermal treatments also increased as compared to the

native starches [9, 10] The increase in thermo-stable SDS

and RS suggests that some interactions formed during

hydrothermal treatments may have survived after

gelatini-zation, thereby partly restricting accessibility of starch

chains to the hydrolysing enzymes [8] The different

chain-length distribution and crystallinity of starch were key

factors for improvement of SDS and RS of treated starch

Hung et al [11] reported that the debranched potato starch

with significantly higher chain length (35.4 glucose units)

formed double helices with more dense crystalline structure

resulting in more resistance to enzyme digestion as

compared to the debranched cassava starch having the

chain length about 32.4 glucose units Partial acid hydrolysis

of starches prior heat–moisture treatments improved RS

yield over the heat–moisture treatments without acid

hydrolysis [12, 13] Rice starch treated with citric acid

followed by heat treatments reduced its RDS content, but

increased its SDS content as compared to control and native

starches [14] The internal structure and physicochemical

properties of the acid and heat treated starches were also

changed such as producing more various short chains,

forming different crystallites that have different melting

temperatures, increasing in apparent amylose content and

cold-water solubility, and decreasing in viscosity and

gel-forming ability [14, 15] Thus, the acid and heat–moisture

treatment not only improves the SDS and RS contents of

starch, but also changes its physicochemical properties In

this study, the effects of a combination of acid and heat–

moisture treatments using various organic acids including

acetic, lactic and citric acids on the formation of SDS and RS,

and physicochemical properties of sweet potato and yam

starches are investigated

2 Materials and methods

2.1 Materials Two kinds of fresh tubers, purple sweet potato (Ipomoea batatas) and yams (Dioscoreaceae atatas) grown in Dong Thap and Long An provinces of Vietnam, respectively, were used in this study and their starches were isolated The purple sweet potato and yam tubers were harvested after planting approximately 3–4 months, depending on each cultivar, soil and growing conditions

Alpha-amylase from A oryzae (30 U/mg) and amylo-glucosidase from A niger (300 U/mL) used in this study were purchased from Sigma–Aldrich Co (St Louis, MO, USA) Other chemicals were purchased from Merck Co (Darmstadt, Germany)

2.2 Starch isolation The starch was isolated according to the method of Lawal [16] with minor modification This traditional method has been widely used to produce the commercial starch products in the traditional craft villages in Vietnam without using chemicals or enzymes to purify starch The purple sweet potato and yam tubers were washed with tap water to remove any type of contamination The cleaned tubers were peeled, sliced and ground with small volumes of distilled water using a Waring blender (7015N, Waring1 Commercial, USA) Then the homogenate was passed through a sieve of 0.232 mm in aperture size The extraction was repeated three times and then the resultant starch slurry wasfiltered through the sieves (0.232 and 0.105 mm in aperture size) and centrifuged at 1500g for 20 min After removing the supernatant, the sediment was washed thoroughly

in distilled water for three times Finally, the starch sediment was recovered and dried in an oven at 40°C for

24 h to 10–11% moisture

After isolation, the starches were analyzed for their chemical composition to evaluate their purity Amylose content of starch was determined according to the method previously descried by Hung et al [17] Protein content was determined using a Kjeldahl digestion system (KI 26, Gerhardt, Germany) based on the standard AACC Approved Method 46-10 [18] Lipid contents were determined by extraction with hexane for 6 h using a Soxhlet apparatus (EV6, Gerhardt, Germany) and ash content was determined by burning in a muffle furnace at 550°C for 3 h [18] Total starch was calculated as follows: total starch (%, db)¼ 100%  protein content (%, db) lipid content (%, db)  ash (%, db) 2.3 Acid and heat–moisture treatments of starches The isolated sweet potato and yam starches (100 g) were directly weighed into screw capped bottles and then

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moisture content of sample was adjusted to 30% by

adding a measured volume of each acid solution (0.2 M

lactic acid, 0.2 M acetic acid, or 0.2 M citric acid) After

dispersion, the bottles were equilibrated at room temperature

for 24 h before heating at 110°C for 8 h After heat–

moisture treatment, the starch samples were neutralized

with 1 M sodium hydroxide and then washed thoroughly

with distilled water The treated starches were recovered

by centrifuging at 10,000g for 30 min and then dried at 40°C

for 24 h

2.4 Determination of starch fractions (RDS, SDS, RS)

Rapid digestible starch (%RDS), slowly digestible starch (%

SDS) and resistant starch (%RS) of the native and treated

sweet potato and yam starches were measured based on the

method of Englyst et al [1] with a moderate modification as

follows Starch (0.3 g, db) was mixed with 20 mL of sodium

acetate buffer (pH 6.0) and then boiled for 30 min in a water

bath The sample was equilibrated at 37°C for 15 min and

then an enzyme solution (5 mL) ofa-amylase (1400 U/mL)

and amyloglucosidase (13 AGU/mL) was added The starch

solution was incubated with shaking at 37°C for 120 min

The total glucose concentrations of the 20 min-digested

and 120 min-digested hydrolysates (G20 and G120,

respec-tively) were determined using the phenol–sulfuric acid

method The remained residue was intensively hydrolyzed

with 7 M KOH and then with amyloglucosidase (50 AGU/

mL) Thefinal hydrolysate was then determined for total

glucose concentration (TG) The values obtained for G20,

G120, and TG were used to calculate for RDS, SDS, and RS

as follows

RDS¼ G20 0:9

SDS¼ ðG120 G20Þ  0:9

RS¼ ðTG  G120Þ  0:9

2.5 Determination of degree of polymerization of

starch

The number-average degrees of polymerization (DPn) of

native and treated starches were determined by the method of

Hizukuri et al [19] DPn was calculated as the difference

between reducing residues and total glucose concentration of

the starches [20]

2.6 Determination of X-ray crystallization of starch

X-ray diffraction analysis was performed using an X-ray

diffractometer (Rigaku Co., Ltd, Rint-2000 type, Tokyo, Japan)

operated at 40 kV and 80 mA Diffractograms were obtained

from 2° 2u to 35° 2u with a scanning speed of 8o/min and

scanning step of 0.02o[20]

2.7 Determination of swelling power of starch Swelling powers of native and treated sweet potato and yam starches were determined according to the method of Sasaki

et al [21] with a slight modification The starch sample (0.16 g, db) was dispersed with distilled water (5 mL) and then heated from 50 to 90°C at 10°C intervals After keeping at those temperatures for 30 min, the heated sample was quickly cooled to room temperature in cold water and centrifuged at 3000g for 15 min The supernatant was carefully removed and swelling power was calculated as described by Hung

et al [17]

2.8 Determination of solubility of starch Solubility (%) of starch was determined according to the methods described by Leach et al [22] with a slight modification The native and treated sweet potato and yam starches (0.5 g) was suspended in 30 mL of distilled water in

50 mL-falcon tubes and heated in a thermostatically controlled water bath for 30 min at different temperature range from 50 to 90°C at 10°C intervals Then the tubes were rapidly cooled to room temperature before centrifuging at 1500g for 30 min Then the supernatant (soluble starch) was poured into an aluminum dish and dried at 120°C for

4 h The solubility of starch was calculated following the formula:

Solubilityð%Þ ¼ m2 m1ðgÞ

mass of starchðgÞ 100 where: m1, the aluminum dish weight; m2, the weight of aluminum dish containing the soluble starch

2.9 Determination of viscosity of starch solution Viscosity of native and treated starches was measured using

a Brookfield Viscometer LVDV-E (Brookfield Engineering Laboratories, USA) according to the official method described by the International Starch Institute with slight modification [11] A starch slurry (2% starch) was cooked in

a boiling water bath for 15 min with continuously stirring and additional 15 min without stirring The paste was cooled down to 50°C and measured the viscosity in centipoises (cP) at 50°C with spindle SC4-18 at a speed

of 50 rpm

2.10 Statistical analysis All tests were performed at least in duplicate Analysis of variance (ANOVA) was performed using Duncan’s multiple-range test to compare treatment means at P< 0.05 using SPSS software (SPSS Inc., USA)

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3 Results and discussion

3.1 Chemical composition of isolated starches

Chemical compositions of starches isolated from sweet

potato and yam tubers are shown in Table 1 The amylose

contents of sweet potato and yam starches were 18.7 and

22.3%, respectively The higher amylose content of yam

starch than that of sweet potato starch was also reported by

Hoover [23] The difference in amylose contents of sweet

potato starch and yam starch might affect RS formation

during acid and heat–moisture treatments and the

physico-chemical properties of the treated starches The native

starches of sweet potato and yam starches isolated by repeated

dispersion and sedimentation in distilled water contained

high levels of proteins (1.1 and 0.8%, respectively) and lipids

(0.9 and 1.3%, respectively), but low amount of ash content

(0.1%) The purity of the isolated sweet potato and yam

starches was not significantly different (97.9 and 97.8%,

respectively)

3.2 Starch fractions (RDS, SDS, RS) of native and

treated starches

Amounts of rapid digestible starch (RDS), SDS, and RS of

native and treated sweet potato and yam starches are given in

Table 2 In native form, sweet potato starch contained higher

amount of RDS and SDS, but lower amount of RS as

compared to those of yam starch The amount of SDS of sweet

potato and yam starches did not change after heat–moisture

treatment, whereas the amount of RS of these starches

significantly increased The higher amount of RS in the heat–

moisture treated yam starch than the heat–moisture treated

sweet potato starch was also observed when these starches

were treated at the same condition A combination of acid and

heat–moisture treatments significantly increased amounts of

SDS and RS as compared to the native or heat–moisture

treatment only For sweet potato starch, the amount of SDS

increased from 6.6% in native form to 13.2, 8.7, and 11.5%

after heat–moisture treatment combined with lactic acid,

acetic acid and citric acid, respectively, while the amount of

RS raised from 14.7 to 40.1, 37.5, and 42.1% at the same treatment condition For yam starch, the amount of SDS increased from 4.7 to 10.0, 11.6, and 11.3% and the amount of

RS increased from 21.6 to 41.0, 39.0, and 46.4% after lactic acid, acetic acid and citric acid and heat–moisture treatments, respectively The results in this study also indicate that treatment with citric acid produced the highest amounts of

RS in sweet potato starch and yam starch (42.1 and 46.4%, respectively), followed by treatment with lactic acid (40.1 and 41.0%, respectively) and with acetic acid (37.5 and 39.0%, respectively) The previous study also reported that high amount of RS (57.5%) in acid-treated lentil starch was obtained by spraying with 2.2 M HCl and incubated at 140°C for 3 h [24] Shin et al [14] also reported that treatment of rice starch with citric acid followed by heat treatments reduced its RDS content, but increased its SDS content as compared to control and native starches The citric acid-treated starch was found to have more various short chains, which are composed of linear or branched chains than did native rice starch [14, 15] The internal structure of the acid-treated rice starch was more or less spherical and composed of a number of double helices [15] Thus, the formation of RS after heat–moisture treatment is due to either improve the order of the crystalline fraction or enhance the proportion of this fraction in starch granules [6] Moreover, the partial acid hydrolysis of starches prior heat–moisture treatment can enhance the mobility of the molecules and allow more

efficient rearrangement, therefore, improved RS yield over the heat–moisture treatments without acid hydrolysis [12, 13] The results show that amount of RS in the treated yam starch was higher than that in the treated sweet potato starch

at the same treatment condition Thus, the differences in internal structures and amylose contents of sweet potato and yam starches affected the formation of RS in these starches during acid and heat–moisture treatments

Table 1 Chemical composition (%, w/w, db) of sweet potato

and yam starches

Amylose content (%) 18.7  0.5 22.3  0.3

SPS, sweet potato starch; YS, yam starch.

All data presented as mean of duplicate experiments  SD.

Table 2 RDS, SDS, and RS contents (%, w/w, db) of native and treated sweet potato and yam starches

Treatment

Native 78.7d 6.6a 14.7a 73.8d 4.7a 21.6a HMT 66.1c 6.7a 27.2b 64.1c 4.9a 31.0b LA–HMT 46.6 a 13.2 d 40.1 d 49.0 b 10.0 b 41.0 d AA–HMT 53.8b 8.7b 37.5c 49.4b 11.6c 39.0c CA–HMT 46.4a 11.5c 42.1e 42.3a 11.3c 46.4e SPS, sweet potato starch; YS, yam starch; LA –HMT, lactic acid and heat –moisture treatment; AA–HMT, acetic acid and heat–moisture treatment; CA –HMT, citric acid and heat–moisture treatment; RDS, rapid digestible starch; SDS, slowly digestible starch; RS, resistant starch.

Data followed by the same superscript letter in the same column are not significantly different (P  0.05).

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3.3 Degree of polymerization of native and treated

starches

Table 3 shows the degrees of polymerization (DPs) of native

and acid-treated sweet potato and yam starches The results

indicate that the sweet potato starch contained longer average

chain length than did the yam starch The longer average

chain length of sweet potato starch as compared to the yam

starch was due to the lower amylose content and the higher

branched chain length distribution of amylopectin existed in

sweet potato starch than those in yam starch [25]

The treatment of the starches with organic acids under

heat–moisture treatment significantly reduced their DPs as

compared to the native starches The DPs of sweet potato

starch reduced from 1059.2 glucose units to 123.3, 370.1, and

49.2 glucose units after treating with lactic acid, acetic acid,

and citric acid, respectively Likewise, the DPs of yam starch

also reduced from 683.5 glucose units to 56.3, 234.7, and 30.6

glucose units after treating with lactic acid, acetic acid and

citric acid, respectively Shin et al [15] reported that the citric

acid-treated starch contained the short chain-length

mole-cules derived from both linear and branched chains from

amylopectin and linear chains from amylose Thus, the

amylose and amylopectin in sweet potato and yam starches

were partially hydrolyzed at different degrees depending on

different kinds of organic acids The results in this study

agreed with other previous reports [15, 26, 27] Among three

organic acids used, the citric acid had the highest impact on

hydrolyzing of hydrocarbon chains in both sweet potato and

yam starches resulting in the lowest DPs, followed by lactic

acid and acetic acid Thus, the increase in RS contents of the

acid and heat–moisture treated starches was due to the

presence of the low-molecular-weight hydrolysates (both

branched and linear structures of amylose and amylopectin)

produced by acid hydrolysis The formation of double helices

and compartmentalization of amylose–amylose,

amylopec-tin–amylopectin, and amylose–amylopectin chains during

heat–moisture treatment were considered to resist to enzyme

hydrolysis, therefore, increase the amounts of SDS and RS in

the treated starches [8, 28]

3.4 X-ray crystallization of starches X-ray diffraction patterns of native and treated sweet potato and yam starches are shown in Fig 1 The native sweet potato starch exhibited the A-type crystal with the major peaks at around d-spacings 5.8 Å (line 3b), 5.2 and 4.8 Å (line 4a, 4b) and 3.8 Å (line 6a), whereas the native yam starch showed the B-type crystal with a peak at 15.8 Å (line 1), a broad medium intensity lines at about 5.9 Å (line 3a, 3b), a strong line at 5.2 Å (line 4a) and a medium intensity double at 4.0 and 3.7 Å (lines 6a, 6b) as classified by Zobel [29] These results are consistent with the previously reported [27] After acid and heat–moisture treatment, the crystalline structure of sweet potato starch, having the A-type crystal, did not change the X-ray diffraction pattern However, the B-type crystalline structure of yam starch after treatment with acid and heat was changed into the C-type structure, which is close to the A-type crystal structure The similar results were obtained for all treated starches The change in crystalline structure of starch from B-type

to A-type after heat–moisture treatment was also observed for potato and yam starches, while other types of starches such as taro, cassava and cereal starches did not have an altered X-ray diffraction pattern after heat–moisture treatment [7, 30] In this study, the partial hydrolysis by organic acids did not affect the crystalline structure of starches even though more short chain-length molecules were produced

3.5 Swelling powers of native and treated starch Figure 2 shows the results of swelling powers of the native and treated sweet potato and yam starches In the native form, the swelling power significantly increased when the heating temperatures increased from 60 to 90°C After acid treatment, the swelling power of the treated starches significantly reduced as compared to that

of the native starch The results indicate that swelling power of the acetic acid-treated slightly increased when heating temperature was higher than 70°C, whereas the starches treated with lactic acid or citric acid hardly swelled even though heating at 90°C The previous studies also reported that the reduction of pasting properties of the acid-treated starches was due to partial acid hydrolysis of amylose and amylopectin in both crystalline and amorphous regions [14, 31] Thus, the less water-holding capacity of the acid and heat–moisture treated starches was due to the presence of the short chain-length molecules produced by acid hydrolysis In addition, the heat–moisture treatment also enhanced interactions between amylose and amylopectin molecules, strength-ened intramolecular bonds and formation of amylose–lipid complexes resulting in reduction in swelling power of the treated starched [32]

Table 3 Degree of polymerization (DPn) of native and treated

sweet potato and yam starches

SPS, sweet potato starch; YS, yam starch; LA –HMT, lactic acid and

heat –moisture treatment; AA–HMT, acetic acid and heat–moisture

treatment; CA –HMT, citric acid and heat–moisture treatment.

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3.6 Solubility of native and treated starches

The solubility degrees of native and treated sweet potato and

yam starches are given in Fig 3 The results show that the

solubility of starch significantly increased after acid

treatment The solubility degrees of starches treated with

different organic acids increased in order: acetic acid< lactic

acid< citric acid These results are positively related to the

DPs of the treated starches Thus, the increase in the solubility of the treated starches was due to the high amount

of short chain amyloses produced by acid hydrolysis, which easily dissociate and diffuse out of granules during swelling [33] In addition, the results also indicate that the solubility degrees of the native and treated potato starches significantly increased at temperature more than 70°C, whereas the solubility degrees of the native and treated yam

Figure 1 X-ray diffraction pattern of native and treated sweet potato and yam starches SPS, sweet potato starch; YS, yam starch; LA-HMT, lactic acid and heat –moisture treatment; AA-HMT, acetic acid and heat–moisture treatment; CA-HMT, citric acid and heat–moisture treatment.

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starches significantly increased when starch solution was

heated at more than 80°C

3.7 Viscosity of starch solution

The viscosities of 2% starch solutions measured using a

Brookfield Viscometer LVDV-E are shown in Fig 4 In the

native form, the native sweet potato starch had significantly

lower viscosity than did the yam starch The results also show

that the viscosities of starch solutions significantly reduced

when starches were treated with different organic acids The

reduction in viscosity was also observed by Haros et al [31] for corn treated with lactic acid and by Shin et al [14] for rice treated with citric acid Thus, the presence of more short chain molecules produced by partial hydrolysis of starch using organic acids resulted in lower the viscosities of the treated starches

4 Conclusions

In this study, organic acids including acetic acid, lactic acid and citric acid were used to partially hydrolyze sweet potato

Figure 2 Swelling power (g/g) of native and treated sweet potato

and yam starches SPS, sweet potato starch; YS, yam starch; LA –

HMT, lactic acid and heat –moisture treatment; AA–HMT, acetic

acid and heat –moisture treatment; CA–HMT, citric acid and heat–

moisture treatment.

Figure 3 Solubility (%, w/w) of native and treated sweet potato and yam starches SPS, sweet potato starch; YS, yam starch; LA – HMT, lactic acid and heat –moisture treatment; AA–HMT, acetic acid and heat –moisture treatment; CA–HMT, citric acid and heat– moisture treatment.

0

5

10

15

20

25

30

Sample

LA-HMT AA-HMT CA-HMT

Figure 4 Viscosity (cP) of native treated sweet potato and yam starches SPS, sweet potato starch; YS, yam starch;

LA –HMT, lactic acid and heat–moisture treatment; AA –HMT, acetic acid and heat– moisture treatment; CA –HMT, citric acid and heat –moisture treatment.

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and yam starches under heat–moisture treatment By a

combination of acid and heat–moisture treatment, the SDS

and RS contents of the starches significantly increased as

compared to the native starch or heat–moisutre treated starch

(control) The physicochemical properties of the starches

were also changed after acid and heat–moisture treatments

The high amounts of SDS and RS in the treated starches are

desired to produce the low-carbohydrate foods, which have

many benefits for diabetes and overweight’s patients As a

result, the combination of acid and heat–moisture treatment

is a useful method to produce higher RS content applied in

functional food processing

This research is funded by the National Foundation for Science

and Technology Development (NAFOSTED) of Vietnam under

grant number 106.99-2012.26

The authors have declared no conflict of interest

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