Resistant Starch Preparation Methods

Resistant Starch Preparation Methods Amir Amini Khoozani, John Birch, and Alaa El-Din Ahmed Bekhit, Department of Food Science, University of Otago, Dunedin, New Zealand © 2018 Elsevier Inc. All rights reserved.

Introduction Resistant Starch Resistant Starch Health Benefits Preparation Methods Conclusion References

1 1 2 2 4 4

Glossary Prebiotic A carbohydrate-based substance which acts as a metabolite for the growth of probiotics. Probiotic Microorganisms living in the large intestine with capability of fermentation and producing short chain acids that exert health benefits from the gastrointestinal system. Resistant starch A part of starch that is resistant to digestion in the small intestine and can be fermented by colon microbiota.

Introduction Due to the importance of prebiotics in prevention of certain diseases, they have increasingly attracted the attention of food technologists (Verma and Banerjee, 2010). Prebiotics are non-digestible oligosaccharides that offer many beneficial effects on the gastrointestinal system. Typical prebiotics are dietary fibers (DF) where the most well-known are inulin, oligosaccharides and resistant starch (RS) (Buttriss and Stokes, 2008). The functional features of RS, together with its potential physiological benefits, provide an opportunity to increase the level of DF in the diet through common foods. However, processing procedures, especially thermal processing, may decrease the RS content of food products, whether naturally containing RS or RS-enriched products (Sullivan et al., 2017). In this respect, researchers started to look for ways to either increase the amount of RS or making it more resistant to processing conditions. In this chapter, in addition to review the preparation methods of RS, health benefits of this unique prebiotic will also be discussed.

Resistant Starch Resistant starch is mainly composed of the linear part of the starch molecule (amylose) which is fermented by probiotics, including Bifidobacterium species in the colon. This gives rise to the production of short chain fatty acids, mainly butyric acid, which plays a significant role in prevention of colorectal cancer. The effective dosage of RS which exerts beneficial health effects was reported as 6–12 g/d, whereas the recommendation for daily intake of another DF was 38 g/d (Fuentes-Zaragoza et al., 2011; Behall et al., 2006). RS naturally occurs in starch-based seeds, cereal grains and cooled heat-treated starchy foods. The highest amount of RS can be found in raw potato with 75 g/100 g (dry basis). Also, green banana is remarkable due to its high RS percentage of about 70 g/100 g of peeled fruit (Wang et al., 2017). There are five types of RS introduced to date. In table 1, types, sources and description of each type are summarized. Table 1

Resistant starch types, description and sources (Milasinovic-Seremesic et al., 2012; Birt et al., 2013; Khalili and Amini, 2015)

Type

Description

Source

RS1 RS2 RS3 RS4

Physically inaccessible in cell walls Granular native starch with high crystalline structure Retrograded starch Chemically modified starch

RS5

Amylose-lipid complex

Grain, legumes, seeds Raw starchy foods (potato, pasta, high-amylose corn, unripe banana) Retrograded starchy foods Esterified, Etherified or phosphorylated cross-linked starch Fatty acid treatment of debranched starch

1

2

Resistant Starch Preparation Methods

Resistant Starch Health Benefits Considering that several digestive diseases are triggered by inadequate or inappropriate diet, increased consumption of indigestible carbohydrates is important. Among numerous DF, RS has approximately half of the calorific value (8 kJ/g) compared with digestible starch (15 kJ/g) (Chen et al., 2017). Numerous health benefits have been shown for RS. In addition to its direct impact on the reduction of the glycemic index, most health effects have been ascribed to the prebiotic nature of RS (Boll et al., 2016). Colonic microbiota, specifically Bifidobacterium bifidum sp., starts to ferment RS into short chain fatty acids. Therefore, with reducing pH level of the environment by the presence of acetic, propionic and butyric acid, the proliferation of carcinomatous cells begins to be prohibited. Some studies have shown a positive effect of RS intake on prevention of colorectal cancer (Homayouni et al., 2014; Malcomson et al., 2015; Amini et al., 2015; Singh et al., 2016; Hung et al., 2016; Yuan et al., 2017; Yin and Zhao, 2017; Panebianco et al., 2017; Cray et al., 2017). As a result, the indirect effects of RS consumption are mostly due to the activity of probiotic microbiota which is illustrated in Fig. 1.

Preparation Methods There are three main strategies to produce resistant starch-rich powdered ingredients: physical, chemical and enzymatic processes. In the physical method, the main procedure is repeated heating–cooling cycles which lead to reorganization of linear chains of starch into a new structure which is resistant to hydrolysis by digestive enzymes (Sarawong et al., 2014). When heating is applied to a high-amylose starch dispersion, disaggregation and breaking of both amylose and amylopectin occurs and leads to formation of shorter linear chains. In the next process, cooling down of these chains brings about the formation of double helical aggregates which are denser and more resistant to be hydrolyzed. Consequently, RS produced by this method is more resistant to heat treatment and can be used as a functional ingredient for fortification of food products (Abioye et al., 2017). Chemical methods promote modification of starch granules by lintnerization, acetylation, phosphorylation, oxidation, hydroxypropylation, esterification and combinations of these treatments (Nagahata et al., 2013). In each of these treatments, a chemical reagent prevents enzymes from binding properly to the starch. For instance, acetyl groups can be esterified to starch using free hydroxyl groups present on the glucose units with acetic anhydride commonly being used (Sha et al., 2012). In oxidation, by the utilization of reagents such as oxygen, ozone, sodium hypochlorite, periodate and hydrogen peroxide, carbonyl and carboxylic groups are produced that impedes the starch digestive enzymes (Chung et al., 2008). For hydroxypropylation treatment, propylene oxide is commonly used. Under high alkaline conditions, the esterified propylene is utilized to free hydroxy groups from the starch structure resulting in a bulky structure which cannot be digested by carbohydrase enzymes (Juansang et al., 2012). Lintnerization is the term applied to mineral acid-treated starch. By disruption of amorphous sections of starch, acid treatment (mainly by

Increase

Figure 1

Decrease

Prevention

excretion rates of cholesterol

postprandial insulin response

colon cancer

mineral absorption

postprandial glucose response

obesity

T-lymphocyte cells

pathogenic growth

hypertention

immune system

duration of rotavirus diarrhea

inflammatory bowel diseases

HDL-Cholesterol

LDL-Cholesterol

type one diabetes

excretion rates of bile acids

appetite

type two diabetes

Health effects of resistant starch (Homayouni et al., 2014; Amini et al., 2015).


Table 2

3

Chemical treatments for the production of resistant starch

Chemical method

Starch type

Main chemical process

Remarks

Reference

Lintnerization

Banana Corn Waxy corn

HCL (heating for 75 C and storage up to 78 h)

• Time consuming and less

Pea Normal corn Canna Rice Wheat

Using sodium trimetaphosphate and sodium tripolyphosphate in alkaline conditions (around 3 h), following gelatinization at 100 C Addition of monochloroacetic acid in alkaline conditions with subsequent microwave treatment Injection of O3, H2O2, O2 in alkaline conditions for 30 min

• Legal limitations by FDA at

Aparicio-Saguilán et al., 2005, Brumovsky and Thompson, 2001, Ozturk et al., 2011, Nagahata et al., 2013 Dupuis et al., 2014, Thompson, 2001, Yeo and Seib, 2009

Phosphorylation

Carboxymethylation

Oxidation

Potato Rice

Normal corn Rice Pinto bean

Acetylation

Hydroxypropylation

Citric Acid treatment

Rice Canna Normal corn Canna Normal corn Waxy corn Normal Waxy Hylon VII

Treatment with vinyl acetate (30 C, 5 h) Addition of propylene oxide in alkaline conditions Followed by gelatinization (40min) 12 h reaction with 0.1 or 0.01 M citric acid followed by oven heating OR Non-autoclaved method: 16 h reaction þ 9 h heating at 120 C

productive

excess amounts (0.4%)

• Destructive effects on

bread’s rheology at high level of substitution

• Reducing process time by microwave heating • Low RS yield

• Enzymatic hydrolysis by

a-amylase • Slightly increase in bean starch • Around 16% vinyl acetate led to higher amount of RS

• Long treatment (40 h) • Decrease of RS compared to initial amount

• Decrease of RS2 amount • Long procedure time • Only suitable for high

Liu et al., 2012, Kittipongpatana and Kittipongpatana, 2013 Chung et al., 2008, Simsek et al., 2012

Sha et al., 2012, Simsek et al., 2012; Juansang et al., 2012 Juansang et al., 2012, Chung et al., 2008, Han and Bemiller, 2007 Sun et al., 2012, Shin et al., 2007, Xie and Liu, 2004

amylose cereals

hydrochloric acid) leaves behind a higher ratio of crystalline parts which are more difficult for enzymes to access. In table 2 some of the main chemical modifications are shown. Enzymatic treatments focus on debranching the a-1-6 amylopectin bonds by pullulanase and isoamylase which results in rearranging the structure later in the retrogradation process (Reddy et al., 2013). Other enzymes such as a and b-amylase are used to hydrolyze the starch amorphous regions and leave a tightly packed crystalline structure behind. Consequently, the aim of using debranching enzymes is to hydrolyze amylopectin branch chains and provide more linear parts (Cai and Shi, 2010). In this regard, subsequent retrogradation will produce higher levels of RS3 with double helical structures stabilized by hydrogen bonds. However, in order to achieve maximum enzyme performance, optimal pH, temperature and time of reaction should be precisely controlled. Table 3 shows the main enzyme processes in enzymatic treatment of starchy crops.

Table 3

Enzymatic treatments for the production of resistant

Enzymatic method

Starch type

Main enzyme process

Remarks

Reference

b-amylase

corn Wheat

• Long preparation procedure • Two-fold increase in RS

Hickman et al., 2009

b-Amylase and Pullulanase Isoamylase

corn starch

20 h of b-amylase reaction followed by 3 autoclave cycles b-Amylase in conjunction with Pullulanase 1g/100 g starch dry basis Isoamylase (50 C, 24 h) followed by retrogradation Pullulanase, 40U/g,10 h followed by heat treatment at 50 C

• Optimum amount of enzyme

Zhang and Jin, 2011

Pullulanase

Waxy corn Waxy wheat Waxy potato Gelatinized red kidney bean Cassava potato

concentration is of importance • Pre-cooking is needed Long post-treatment (48 h) • Significantly increased RS3 • Thermal treatment is needed • Long post-treatment (24h/25 C)

Cai and Shi, 2010

Reddy et al., 2013, van Hung et al., 2012

4


Table 4

Combination treatments for increasing resistant starch

Source

Procedure

%RS (g/100 g)

Remarks

Reference

Taro corm

autoclaving, enzymatic debranching, retrogradation and oven drying processes for two times (60 C) twin-screw extrusion, cooking, mild acid hydrolysis, hydrothermal treatments (110 C) enzymatic debranching, steam cooking, drying (45 C) and freezing (28 C) storage in 23 C then drying at 50 C after each extrusion cooking with high moisture feed for 3 cycles

35.1 1.9% (dry basis)

• A combination of methods in

Simsek and El, 2012

Maize starch

Cassava starch

High amylose corn starch (Hylon V and VII)

High-amylose corn starch

Hydrothermal Pressure (15 MPa for 2 h) followed by retrogradation (120 C/24h, 4 C)

two cycles resulted in 16-fold increase in RS amount

increased from 11% to 20%

• Acid modified normal-maize

Hasjim and Jane, 2009

starch (AMMS) produced a greater RS 19–20

Hylon V: from 43 to 40 Hylon VII: from 53 to 45.1

At 100 C reached to 27%

• Refrigeration of cassava starch gave rise to higher RS compared to freezing storage • RS3 made from Hylon VII had high emulsion stability • Repeated autoclavingstorage cycles are necessary to increase the RS3 content to the desired levels • The hydrothermal pressure resulted in a significant increase in the total RS content if the samples were gelatinized at temperatures below 120 C

Abioye et al., 2017

Masatcioglu et al., 2017

Pu et al., 2013

Regarding that a combination of mentioned methods could also increase the RS amount, most of them ended with retrogradation processes resulting in RS3 increments. The conditions and percentage of produced RS3 in the finished product are summarized in table 4.

Conclusion Resistant starch is an exceptional prebiotic with numerous additional health benefits. It also brings technological positive effects for food products as a functional ingredient. However, processing conditions, especially heat treatment, can attenuate its content. Consequently, there are ways in order to isolate and increase the amount of resistant starch with the aim of increasing its capability to be resistant during food processes. Chemical reagents could increase the amount of resistant starch type four in starchy foods, however, long reaction times and some health concerns about the dosage of chemicals and the residue are limiting factors. Enzymatic debranching is shown to be more effective due to the high concentration of produced resistant starch type three. It also seems to be an essential step when used with other methods, such as heat and cool cycles. Though, it needs a controlled environment, effective enzyme activity and subsequent heat treatments. Although the heating–cooling cycles could increase the resistant starch type three in produced products, there are several factors that needed to be investigated including the rate of cooling/heating process, number of cycles and various temperatures. Additionally, the combination effect of fatty acid addition and other methods for producing resistant starch type five has not been considered yet.

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