CHAPTER IINTRODUCTION

1.1. BackgroundStarch is a carbohydrate (polysaccharide) which produced by green plants through photosynthesis, and stored in tubers, seeds, stems, or fruits. Plants which generally have a high starch content are cereals and tubers. However, many fruits also have a fairly high starch content, one of them is banana. The usage of starch is very knowledgeable both in people's daily life and in the food processing industry. Natural starch (native starch) is causing some problems related to the retrogradation, low stability and low durability paste. It became the reason for the modification starch (Waliszewski et al., 2002). Modified starch has been developed for a very long time and its application in the food industry which is really significant today.According to Zulaidah (2012), modified starch is starch which the hydroxyl groups have been modified through a chemical reaction or by disrupting its original structure. Certain starch treated with the aim of producing better properties to improve the properties of the previous or to change some properties of the previous or other properties.Banana (Musa paradisiaca), the largest herbaceous plant in the world, grown abundantly in many developing countries is considered to be one of the most important sources of energy for people living in the humid regions of many countries (Waliszewski, dkk., 2002). Banana has excellent nutritional content and gives a quite high energy compared to other fruits. Bananas are rich in minerals such potassium, magnesium, phosphorus, iron, and calcium (Munadjim, 1983). The content of inulin (approximately 3%) found in bananas is also beneficial as a natural prebiotic (Nuraida, 2011).Bananas also have fairly high starch content is about 61-73% for this type of banana: kepok, siam, uli and tanduk. High starch content in bananas is potential to be modified and produce a modified starch which has prebiotic properties. Banana modified starch called Resistant Starch (RS). The problems that arise are not many people who know what RS is, especially with its benefits.1.2. Problem IdentificationThe problems that can be identified from this paper are:1. How to modify the banana starch?2. What are the types, characteristics and benefits of banana modified banana starch, and its application in the food industry? 3. What are the benefits of modified banana starch for human health?4. How to increase the amount of resistant starch type 3 (RS3)?

1.3. ObjectivesThe purposes of writing this paper are:1. Provide information about how to modify the banana starch.2. Knowing the types, characteristics and benefits of modified banana starch, and its application in the food industry.3. Knowing the benefits of modified banana starch for human health.4. Knowing how to increase the amount of resistant starch type 3 (RS3).

1.4. GoalsThe goals of writing this paper are to inform the readers about the advantages of modified starch and resistant starch in food industries and for human health compared with the native starch, in order that the readers can use those starches in making products.

1.5. Method of WritingMethod of writing is conducted with the literature review method. Literature review method is directed to search through the data and documents, such as written documents, images, and electronic documents which can support the writing process.

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CHAPTER IILITERATURE REVIEW

2.1. BananaBanana (Musa paradisiaca) is one of Indonesian horticultural products which have high economic value because of its availability is not depending on the season and the the price is affordable. The advantages of banana is as a source of carbohydrates, vitamins and minerals are also supported by the harvested area and the amount of production which always occupies the first position. Banana productivity in Indonesia is fluctuating and rising, where in 2007 the level of banana production is 5,454,226 tons, then in 2008 increased to 6,004,615 tons (Munadjim, 1983).Bananas have excellent nutritional content and provide high energy compared to other fruits. Bananas are rich in minerals such potassium, magnesium, phosphorus, iron, and calcium. The content of inulin (approximately 3%) found in bananas also act as a natural prebiotic. Besides inulin, bananas also have a fairly high starch content is about 61-73% for kapok, siam, uli and tanduk banana. High starch content in bananas is potential to be modified becomes RS which also have prebiotic properties. Prebiotic effect is not just limited to the RS which are naturally present in plant (RS1 and RS2), but also owned by the physically and chemically modified starches (RS3 and RS4) (Munajdim, 1983).Banana plants flowering at the age of 9-12 months after planting. Cutting bunches conducted at the age of 80-110 days after flowering and usually at the age of 110 days when the bananas color begins turn to yellow. Sizes, colors and flavors of banana fruit varies depending on the variety. Moreover, growth of banana plants affected by soil conditions, climate and way of maintenance. Based on how it is used, bananas are classified into two categories, banana and plantain. Banana is group of bananas are eaten in fresh form (ripe fruit), for example ambon, raja sereh, raja bulu, susu, seribu, and others. Plantain is a group of bananas are eaten after being processed first, for example uli, kepok, siam, kapas, rotan, tanduk, and others (Munadjim, 1983).

2.2. Resistant StarchRS includes the portion of starch that can resist digestion by human pancreatic amylase in the small intestine and thus, reach the colon. The general behaviour of RS is physiologically similar to that of soluble, fermentable fibre. like guar gum. The most common results include increased fecal bulk and lower colonic pH and improvements in glycemic control, bowel health, and cardiovascular disease risk factors, so it has shown to behave more like compounds traditionally referred to as dietary fibre (Fuentes-Zaragoza, et al., 2011).RS is the fraction of starch which is not hydrolyzed to D-glucose in the small intestine within 120 min of being consumed, but which is fermented in the colon. Many studies have shown that RS is a linear molecule of a-1,4-D-glucan, essentially derived from the retrograded AM fraction, and has a relatively low MW (1.2 _ 105 Da). RS is an extremely broad and diverse range of materials and a number of different types exist. At present, these are mostly defined according to physical and chemical characteristics (Sharma, et al., 2008 ; Haralampu, 2000).A number of factors may cause starch to be resistant to digestion, including the size of the starch-containing fragments (such as coarsely ground grains), the structure and conformation of intact starch granules, and the formation of retrograded crystallites as a result of processing and chemical modification. RS is found in many common foods, including grains, cereals, vegetables (especially potatoes), legumes, seeds, and some nuts (Goldring, 2004).According to Fuentes-Zaragoza, et al. (2011), RS has been classified into five general subtypes named RS1RS5, which are described below:1. Type 1 (RS1) includes physically inaccessible starch that is locked within cell walls and food matrixes, thus preventing amylolysis. Milling and chewing can make these starches more accessible and less resistant. RS1 is heat stable in most normal cooking operations, which enables its use as an ingredient in a wide variety of conventional foods.2. Type 2 (RS2) is composed of native starch granules from certain plants containing uncooked starch or starch that was gelatinized poorly and hydrolyzed slowly by R-amylases (e.g., high-AM corn starches). RS2 describes native starch granules that are protected from digestion by the conformation or structure of the starch granule. This compact structure limits the accessibility of digestive enzymes (has low bioaccesibility), various amylases, and accounts for the resistant nature of RS2 such as, ungelatinized starch. In the diet, raw starch is consumed in foods like banana. A particular type of RS2 is unique as it retains its structure and resistance even during the processing and preparation of many foods. This RS2 called high-AM maize starch.3. Type 3 (RS3) refers to retrograded or crystalline non-granular starch formed after cooking, like the starch found in cooked and cooled potatoes, bread crusts, cornflakes, and retrograded high AM maize starch. RS3 refers to non-granular starch-derived materials that resist digestion. RS3 is of particular interest, because of its thermal stability. This allows it to be stable in most normal cooking operations, and enables its use as an ingredient in a wide variety of conventional foods (Haralampu, 2000). During food processing, in most cases in which heat and moisture are involved, RS1 and RS2 can be destroyed, but RS3 can be formed.Storey et al. (2007) classified a soluble polysaccharide called retrograded resistant maltodextrins as type 3 RS. They are derived from starch that is processed to purposefully rearrange or hydrolyze starch molecules, and subsequent retrogradation, to render them soluble and resistant to digestion. This process results in the formation of indigestible crystallites that have a molecular similarity to type 3 RS but with a smaller degree of polymerization as well as a lower MW, converting a portion of the normal alpha- 1,4-glucose linkages to random 1,2-, 1,3-, and 1,4-alpha or beta linkages.4. Type 4 (RS4) includes chemically modified or re-polymerized starches (e.g., chain linkage altered dextrins, ethers, or esters) used by food manufacturers to alter the functional characteristics of the starch, and include starches which have been etherized, esterified, or cross-bonded with chemicals in such a manner as to decrease their digestibility. RS4 can be produced by chemical modifications, such as conversion, substitution, or cross-linking, which can prevent its digestion by blocking enzyme access and forming atypical linkages.5. Type 5 (RS5) is an AM-lipid complexes starch, which is formed from high AM starches that require higher temperatures for gelatinization and are more susceptible to retrograde. In general, the structure and amount of starch-lipid in foods depend on their botanical sources. Also, Frohberg and Quanz defined as RS5 a polysaccharide that consists of water-insoluble linear polyalpha-1,4-glucan that is not susceptible to degradation by alpha-amylases. They also found that the poly-alpha-1,4-D-glucans promote the formation of short-chain fatty acids (SCFA), particularly butyrate, in the colon and are thus suitable for use as nutritional supplements for the prevention of colorectal diseases.From all types of RS, RS3 is the most interesting because this RS type can retain the organoleptic characteristics of the food when the RS3 added to food. The content of RS3 in food could be improved with some treatments, such as autoclaving, treatment with enzymes, processing and fermentation. Heat treatment using autoclaving method can increase the production of RS up to 9% (Sajilata, et al., 2006). Different banana varieties have different levels of RS (Musita, 2009). The yield of starch and resistant starch content of different varieties of bananas can be seen in Figure 1.

VarietiesFigure 1. The yield of starch and resistant starch content of different varieties of bananas (Musita, 2009).

2.3. Starch ModificationStarch has been widely used in food processing, both in use in the food industry and the household scale industry. Starch which is used usually a of starch without modification treatment (native starch). Although natural starch quite flexible in its use, but has disadvantages that often inhibit its application in food processing. Most natural starch produces starch suspension with a viscosity and the ability to form gels that are not uniform (inconsistent). This is due to the natural starch gelatinization profile is strongly influenced by climatic and physiological condition of the plant so that the same type of starch do not necessarily have the same functional properties (Zulaidah, 2012). According to Widianingrum (2012), the main disadvantages are as follows: 1) Most of the natural starch cannot stand the high temperature heating, 2) most of the natural starch cannot stand under acidic conditions, 3) a natural starch cannot stand the mechanical process (agitation), where the viscosity of starch will be decreased due to stirring or pumping process, 4) a natural starch is limited in water solubility, and 5) a natural starch gel prone to syneresis (separation of water from the gel structure) due to starch retrogradation.Natural starches are often modified to produce starch in accordance with the conditions of processing. Starch modification is done to overcome the unfavorable fundamental properties of natural starch so it can expand its use in food processing and produces the desired characteristics of food products. Starch was given particular treatment in order to have better properties to improve the previous properties, especially the physicochemical and functional properties or to change some other properties. Some of origin natural starch properties which can be modified are gelatinization temperature, characteristics during gelatinization process, warming, acidification and stirring durability, and retrogradation tendency. Modification done at the molecular level with or without changing the structure of the starch granules (Zulaidah, 2012)

2.4. Industrial Applications of Modified StarchStarch plays an important role in the food processing industry and other industries such the manufacture of paper, glue, textile, drilling mud, candy, glucose, dextrose, fructose syrup, and others. In trading, there are two kinds of starch, unmodified and modified starch. Starch which has not been modified or regular starch is all kinds of starches which produced with basic processing plants e.g. tapioca flour. According to Pudjihastuti (2010), a natural starch has several problems when used as raw materials in the food and non-food industries. When was cooked, starch takes a long time (needs high energy), also formed a hard paste and less transparent. Besides, its too sticky and less resistant to acid treatment. These constraints cause the natural starch is limited in its use in industry. Though the source and starch production in our country is very abundant, consisting of tapioca (cassava starch), sago starch, rice starch, tubers starch, fruit starch (e.g. banana starch) and more sources of starch have not been produced commercially.On the other hand, industrial starch users want starch which have stable viscosity both in high and low temperatures, have good resistance to mechanical treatment, and the power coagulation resistant with acidic conditions and high temperatures. Important properties desired of modified starch (which not owned by natural starch) are: higher brightness (whiter starch), low retrogradation, lower viscosity, gels formed more clear, gels texture formed more flabby, low tensile strength, starch granule friable, higher gelatinization time and temperature, and lower time and temperature needed to rupture (Pudjihastuti, 2010).

CHAPTER IIIDISCUSSION

3.1. High-Resistant Starch Banana CharacteristicsBananas which are still green (unripe), hard textured, and was about 90 days (3 months) from the flowering time, contain high amounts of resistant starch compared with perfectly ripe banana (Waliszewski, et al, 2002). The biggest carbohydrate component in banana is the starch in its flesh, will be hydrolized into simpler sugars when banana is ripe through the process of respiration, so the starch content decreased. Plaintain banana (consumed after cooked), such kepok, tanduk, and janten bananas contain more starch than the banana fruit (consumed directly) such as ambon, raja, muli, and other bananas. Banana starch content in fresh plaintain banana ranged from 61.3 - 76.5% dry basis. If the starch content is high, the resistant starch content will be higher. Medium size raw banana contains about 4.7 grams RS2 (Nurhayati, 2010).

3.2. Banana Starch Modification MethodsAccording to Zulaidah (2012), there are several ways which can be used to modify banana starch into resistant starch (RS), such as chemical, physical and conventional modification. Chemical modification includes the addition of acid, enzymatic hydrolysis, and cross-linking. Physical modification includes extrusion, parboiling, steam-cooking, microwave irradiation, roasting, hydrothermal treatment and autoclaving (Widianingrum, 2012).

3.2.1. Chemical Modification3.2.1.1. Acid TreatmentAcid hydrolysis method is done by using a strong acid, which will hydrolyze glycoside bonds which will shorten the chain of chemical bonds in starch and starch molecular weight becomes lighter (Widianingrum, 2012). Acid modified starch prepared by hydrolyzing starch with acid under gelatinization temperature, at a temperature of about 52oC. Basic reaction includes cutting -1,4-glucosidic bonds from amylose and -1,6-D-glucosidic from amylopectin, so the size of the starch molecules becomes smaller and increase the tendency to form gels paste (Zulaidah, 2012).According to Widianingrum (2012), in the early stages of acid modification process, the amount of amylose or linear fraction increases, which indicates that the acid hydrolyzes the end points of amylopectin branches in amorphous regions which easily reached before hydrolyzes the crystalline section. It is proved by the absence of starch granule swelling and starch do not lose its crystalline properties. Amorphous part is composed of much amylose chains, while the crystals are composed of much chains of amylopectin. Acid hydrolyzes the starch granules amorphous parts faster, but the part which is tiered neat (crystalline) is slowly hydrolyzed.Acid modified starch have lower hot paste viscosity, larger retrogradation tendency, cold starch paste viscosity ratio is lower than the hot starch paste, granule which swell during gelatinization in hot water is lower, stability increase in warm water under gelatinization temperature and alkaline numbers is higher. In acid hydrolysis method, acid concentration, temperature, starch concentration and reaction time may vary depending from the desired properties of starch. Amylose molecules is easily breakable compared with amylopektin molecule so the acid modification will lower amylose group. Compared with the original starch, acid modified starch shows different properties, such viscosity reduction thus allowing the use of starch in larger quantities, decrease the binding ability of iodine, swelling reduction of granule during gelatinization, intrinsic viscosity reduction, increase the solubility in hot water under gelatinization temperature, lower gelatinization temperature, decrease osmotic pressure (molecular weight loss), increase the viscosity ratio of hot against cold viscosity and increased absorption of sodium hydroxide/NaOH (alkaline number is higher). But just as natural starch, modified starch is insoluble in cold water (Zulaidah, 2012). Acid modified starch reaction is shown in Figure 2.

Figure 2. Acid modified starch reaction (Zulaidah, 2012).3.2.1.2. Enzymatic ModificationThis involves the exposure of starch suspensions to a no of enzymes primarily including hydrolyzing enzymes that tend to produce highly functional derivatives. Origin of this technique can be dated back to the times when glucose syrup or high fructose corn syrup was produced. The enzymes amylomaltases(-1,4-1,4 glucosyl transferases) found in eukarya, bacteria and archea representatives, breaks an -1,4 bond between two glucose units to subsequently make a novel -1,4 bond producing a modified starch that can be used in foodstuffs, cosmetics, pharmaceutics, detergents, adhesives and drilling fluids. It is also a good source of plant-derived substitute for gelatin except that it forms a turbid gel whereas gelatin gels are transparent (Neelam, et al., 2012).

3.2.1.3. Cross-Linking ModificationCross-linking reinforces the hydrogen bonds in the granule with chemical bonds that act as a bridge between the starch molecules. Important factors in the cross-linking reaction include chemical composition of reagent, reagent concentration, pH, reaction time and temperature. Because the degree of cross-linking for food starch is very low, the extent of reaction and yield of cross-linked starch are difficult to measure chemically; hence there is a need for physical property measurement. When phosphorus oxy chloride (phosphoryl chloride, POCl, MW153.3) is added to starch slurry under alkaline conditions (pH 812), the hydrophilic phosphorus group immediately reacts with the starch hydroxyls, forming a distarch phosphate (Neelam, et al., 2012).Cross-linking alters, not only the physical properties, but also the thermal transition characteristics of starch, although the effect of cross-linking depends on the botanical source of the starch and the cross-linking agent. Decrease in retrogradation rate and increase in gelatinization temperature has been observed with cross-linked starch, and these phenomena are related to the reduced mobility of amorphous chains in the starch granule as a result of intermolecular bridges However, cross-linked starch has more pronounced syneresis than has native starch because of ordered structure in the starch paste, thus resulting in a higher degree of retrogradation (Neelam, et al., 2012). Cross-linking reaction is shown at Figure 3.

Figure 3.Cross-linking reaction (Zulaidah, 2012).

3.2.2. Physical ModificationPhysically modified starch treatment involves several factors such as: temperature, pressure, and water content in starch. Starch granules can be totally or partially modified. The principle of general physical modification is by heating. When compared to chemical modification, physical modification tend to be more secure because it does not use a variety of chemical reagents. Physical modification treatment include: extrusion, parboiling, steam-cooking, microwave irradiation, roasting, hydrotermal treatment and autoclaving. Most of the physical modification methods mentioned may increase levels of the RS3. Steaming-cooking method and is generally applied to the rice parboiling. Extrusion method is the most popular method used to modify the functional characteristics of cereal starch. The process uses high temperature, short time, and starch gelatinization occurs in low water content (Widianingrum, 2012).According to Adobowale, et al. (2005), hydrothermal-treatment method consists of annealing and heat moisture treatment (HMT). The principle of hydrothermal-treatment method is the use of water and heat to modify starch. On annealing, the modification is done by using large quantities of water (more of 40%) and heated at a temperature below the gelatinization temperature starch, while HMT performed using a limited amount of water content (18, 21, 24, 27%) and heated at a temperature exceeds the gelatinization temperature. Hydrotermal-treatment method can change the starch gelatinization characteristics that increase the gelatinization temperature, starch paste viscosity increases, and increases the tendency to undergo starch retrogradation.Other physical treatment is autoclaving-cooling method. According to Sajilata et al (2006), the heating treatment using autoclaving-cooling method can increase the production of the RS3 up to 9%. Autoclaving-cooling method performed by suspending starch with the ratio of water addition is 1: 3.5 or 1: 5 (w / v). Furthermore, using the autoclave is heated at high temperatures. After autoclaving, the starch suspension is stored at low temperature to occur retrogradation. To increase levels of the RS3, the cycle is repeated. This modification treatment called autoclaving-cooling cycling treatment (Widianingrum, 2012).

3.3. Improving The Amount of RS3 in BananaIncreasing production of RS3 is by modifying the banana starch with debranching and retrogradation process at different storage conditions and with autoclaving-cooling.

3.3.1. Autoclaving-coolingAccording Jenie, et al. (2012), autoclave heating and the addition of 0.2% POCl3 can increase level RS3 and RS4, and can be utilized by Lactobacillus casei, L. plantarum, Bifidobacterium bifidum and as a prebiotic in vitro. Autoclave heating cause banana starch gelatinization and retrogradation in banana slices during 24 hours of storage at room temperature ( 30C). Banana starch gelatinization cause damage to the banana starch (changes in structure of granules), resulting in degradation of starch content and amylose fraction leak out causes the starch granules and dispersed in water. However, after retrogradation phase, hydrogen bonds in amylose have dropped back to bind and form a new structure (amorphous into crystalline structure) and stable. Debranching of amylopectin increases RS levels significantly due to the linear molecule derived from amylopectin has a role in retrogradation.

3.3.2. Debranching and Retrogradation at Different Storage ConditionThe amount of RS was improved by debranching and retrogradation at different storage condition. The banana starch after debranching and storing at -18oC had the highest RS content, which can be used as a functional food with high health benefits. The banana starches, which were gelatinized and retrograded by autoclaving treatment and storing at the different temperatures without debranching, had the C-type crystalline structures similar to the native starch. However, the crystallinities of the debranched banana starches changed to the typical B-type crystalline structure for all samples at different retrogradation conditions. These results are due to the re-organization of the short linear chain molecules during the retrogradation process (Hung, et al., 2013).The degrees of crystallinity of the gelatinized starches stored at 4oC and -18oC were significantly higher than that of the native starch or the gelatinized starch stored at 25oC, whereas the degrees of crystallinity of the debranched starch at different storage temperatures were significantly higher than that of the native starch which is shown in Table 1. The native banana starch analyzed as eaten sample had a high amount of RS (11.2%), which was higher than did cassava and potato

Table 1. Degree of crystallinity of native and debranched banana starch.

Source: Hung, et al. (2013)

RS concentrations of the native, gelatinized and debranched starches are given in Figure 4.

Figure 4. Resistant starch concentrations of native and debranched banana starches at different storage conditions (Hung, et al., 2013).

3.4. Swelling PowerSwelling power is the starch ability to swell. The factors which affect are amylose-amylopectin ratio, chain length, and molecular weight distribution (Pudjihastuti, 2010). Swelling power of starch was reported to be inhibited by amylose and lipids (Tester and Morrison, 1990). The swelling powers of the banana starches were significantly lower than those of the cassava starches. Banana starch had the swelling power and solubility close to those of sorghum starch, but significantly lower than those of tapioca and potato starches (Kayisu, et al., 1981). The interaction between starch chains within both the amorphous and crystalline domains is responsible for the swelling power and solubility of starch (Zhang, et al., 2005). The different amylase content, molecular weight distribution, degree of branching, length of branches and conformation of the molecules affected the swelling power and solubility of starch (Ratnayake, et al., 2002). In addition, the amylose-lipid complexes or protein within granules is also influenced in these properties (Hoover and Hadziyev, 1981). The swelling powers of banana starches were also not significantly different when cooking at different temperatures (Hung, et al., 2013).According to Musita (2009), varieties of banana very significant effected on water absorption and swelling power of banana resistant starch. Observation of the water absorption of some varieties of banana resistant starch is presented in Figure 5 and the swelling power in Figure 6.

Varieties

Figure 5. Water absorption of resistant starch from various varieties of bananas (Musita, 2009).

VarietiesFigure 6. Swelling power of resistant starch from various varieties of bananas (Musita, 2009).

3.5. Gel CapacityResistant starch of ambon, batu, kepok kuning, raja bulu, and tanduk bananas cannot form gels at of 8% concentration, while at the same concentration, the banana starch slightly form gels. This indicates that resistant starch from five types of bananas are classified into RS2 (ungelatinized starch) (Haralampu, 2000). Gels forming ability of the banana starch and resistant starch can be seen in Table 2.

Table 2. Gels forming ability of the banana starch and resistant starch.Type of BananaBanana StarchResistant Starch

123123

Ambon(*)(*)(*)(-)(-)(-)

Batu(*)(*)(*)(-)(-)(-)

Kepok Kuning(*)(*)(*)(-)(-)(-)

Raja Bulu(*)(*)(*)(-)(-)(-)

Tanduk(*)(*)(*)(-)(-)(-)

(*) = slightly forms gels at 8% concentration.(-) = Do not form gels at 8% concentration.Source: Musita (2009)Starch consists of tiny droplets called granule. Starch which is generally when dissolved in water (approximately 8-12% solution) and heated will undergo a process called gelatinization which would increase the disintegration of granules so the starch molecules will be more digestible. Starch consists of tiny droplets called granule. Starch which is generally when dissolved in water (approximately 8-12% solution) and heated will undergo a process called gelatinization which would increase the disintegration of granule so the molecules will be more digestible starch. The results showed that the resistant starch which has been isolated from banana starch after diluted with water (concentration 8%) and heated to boil do not form gels but is viscous. Viscous properties of resistant starch as a water-soluble dietary fiber that can inhibit the digestion and absorption of carbohydrates in the small intestine. Condensed form will cause an improvement to the thickness of the layer between food and the brush-border surface in the small intestine, preventing the absorption of nutrients, including glucose so the glycemic index value is low (Musita, 2009).The ability of starch to form a gel can be influenced by the chemical composition of starch itself such a comparison between the content of amylose and amylopectin and also starch granule size (Tester, 1997). Starch with small granule size will be more susceptible to gelatinization process. In addition, a comparison between the amorphous and crystalline parts also affects the gelatinization. The higher amorphous part of the starch will be more susceptible to gelatinization process because amorphous part can absorb more water so starch granules will swell and form gels. In the amorphous, amylose content of much more than the content of amylopectin (Jane and Chen, 1992). Loesecke research results (1950) shows the proportion of amylose 20.5% and amylopectin 79.5% on fresh banana fruit. Resistant starch of ambon, batu, kepok kuning, raja bulu, and tanduk bananas are suspected have high crystalline portion and amylopectin content of many that it is difficult form gels.Gonzlez-Soto, et al. (2006) showed banana starch gelatinization temperature is higher than corn starch and starch mango, yaiu 76.3 0,06oC and enthalpy of 11.8 0.64 J/g. According to Lii and Chang (1991), banana starch gelatinization temperature is relatively high compared with the starch of tubers, suspected due to the relatively high phosphorus content (0.05 to 0.07 mg / g), phosphorus was suspected esterificated with starch granules so strengthen the structure of starch granules.

3.6. Health Benefits of Banana Resistant Starch3.6.1. PrebioticPrebiotics are utilized to promote the survival of probiotics. Prebiotics are nondigestible carbohydrates that are not absorbed in the intestine, such as RS. RS is not absorbed in the small intestine; it provides the colonic microbiota with a fermentable carbohydrate substrate. It has been suggested that RS promotes a higher proportion of butyric acid than other indigestible carbohydrates. Butyrate constitutes a major energy substrate for the colonocytes and is associated with benefits in relation to colonic health. They travel to the colon where they promote the growth of specific advantageous microbiota (probiotics) by supplying food or energy, while simultaneously influencing the microbiotas gene expression. Starch processing can increase its prebiotic properties (Fuentes-Zaragoza et al., 2011). The possible applications of RS such as prebiotic constituents in functional food formulations could be summarized (Charalampopoulos, et al., 2002):1. as fermentable substrates for growth of probiotic microbiota, especially lactobacilli and bifidobacteria2. as dietary fibre promoting several beneficial physiological effects3. as encapsulation materials for probiotic in order to enhance their stability.Scientific interest upon RS has increased significantly during the last decades, mostly due to its capacity to produce a large amount of butyrate all along the colon. Butyrate has been observed to have a range of effects on cell metabolism, differentiation, and cell growth as well as inhibition of a variety of factors that underlie the initiation, progression, and growth of colon tumors. RS III is fermented by the microbiota in the colon, and it indicates that it may have health benefits such as modifying lipid metabolism and reducing the risk of colon cancer (Champ, et al., 2003).

3.6.2. Disease PreventionRS may be beneficial in disease prevention, including modulation of glycaemic index (GI), diabetes, cholesterol lowering capability and weight management (Zhang, et al., 2005; Sajilata, et al., 2006). As RS passes through to the large intestine where it is bacterially fermented, it lowers the colonic pH as the resultant short-chain fatty acids (SCFAs) are produced and absorbed. The three main SCFAs produced are acetate, propionate and butyrate (Sajilata, et al., 2006; Birkett and Brown, 2007). Butyrate is commonly in high concentrations and is the main energy substrate for colonic cells; it regulates intestinal cell function and growth by repressing tumor cells and reducing the proliferation of colonic mucosal cells, which is a risk factor in carcinogenesis. Acetate and propionate are energy sources for the body, and are thought to play a role in carbohydrate (glucose) and lipid metabolism, particularly in the liver, muscle and adipose tissue, and influence weight management (Thakorlal, et al., 2010).Evidence is increasing with regards to an inverse relationship between starch intake and colon cancer. Butyrate is thought to be associated with lower incidences of colon cancer and a lack of butyrate may increase the risk of some colonic pathologies and inflammatory diseases. RS also acts as a laxative as it reduces intestinal transit time and increases faecal bulk and can be used in products for celiac disease. Recently RS has been classified as a prebiotic, as it beneficially affects the host by selectively stimulating the growth and activity of the microflora in the colon, and thus improving the hosts health (Sajilata, et al., 2006).Since RS is slowly digested, it influences the rate at which glucose is released. Slow release of glucose evokes a small increase in blood glucose (hypoglycemic effect) as it is metabolized five to seven hours after consumption, whereas normally cooked starch is digested immediately. This slow digestion reduces postprandial glycemia and insulinaemia (decreasing blood glucose, insulin and epinephrine levels). RS also has the potential for increasing the period of satiety by reducing the rate of gastric emptying and plays a role in providing improved metabolic control in non-insulin dependent type II diabetes (Bjork, 2006). Hypocholesterolaemic effects of RS diets have been reported. Such diets noticeably increase the feces size, pool and absorption of SCFAs and lower plasma cholesterol and triglycerides. The hypocholesterolaemic properties suggest the use of RS in foods can improve cardiovascular health (Sajilata et al., 2006).In weight management, RS has two main roles with regards to energy metabolism and metabolic control (Birkett and Brown, 2007). Firstly, the digestible energy available from RS is reduced in comparison with a readily digestible starch and hence lowers caloric density. Secondly, the lower glucose and insulin impact of RS causes changes in lipid metabolism that favors lower lipid production, storage and increase fat burning. Important consideration is required in both choice of food and in the selection of specific ingredients to assist with targeting weight management regimes and improving overall health. RS is a versatile option for formulating high quality foods with added health benefits (Thakorlal, et al., 2010).

3.7. Food Industrial Applications of Banana Resistant Starch3.7.1. As Texture ImproversSeveral studies have been carried out on the potential use of modified starches as texture improver in the food industry. It can provide crispness of crackers and biscuits, viscosity breakdown resistant for can foods, desired chewiness for certain foods and improvement in the quality of extruded products.

3.7.1.1. Crispy SnackSanz, et al. (2008) had done some tests of using resistant starch known as RS3 as part of non pre-frying batter for fried squid rings. After frying, the batter crust hardness and fragility were significantly increased with more intense brown-gold color. It was found that good batter performance during the manufacturing process without pre-drying depends on the successful development of thermo gelling property of methyl cellulose (MC). They observed that RS3 did not interfere with the above process as well as did not affect the viscoelastic properties significantly. RS3 was suggested to be used in fried batter food prepared by a processwithout pre-frying (Abbas, et al., 2010).

3.7.2. For High Nutritional ClaimResistant starch is claimed as a functional fiber since it allows high fiber nutritional claim and is well suited for food applications. It is starch that escapes digestion in the small intestine of healthy individuals. Resistant starch is considered the third type of dietary fiber, as it can deliver some of the benefits of insoluble fiber and some of the benefits of soluble fiber. It has many advantages compared to traditional source of fiber due to it smaller crystallites which has low water-holding capacity, small particle size and bland flavor (Sajilata and Singhal, 2004). Commercial resistant starch is a special high-amylose starch that has been modified by biochemical or physical processing to maximize its total dietary fiber content (Abbas, et al., 2010).

3.7.2.1. Slow Digestible CookiesSaguiln, et al. (2007) used resistant-starch rich powder (RSRP) prepared from autoclave-treated linnerized banana starch in the making of slow digestible cookies. The chemical compositions, rate of starch digestion in vitro and the acceptance of RSRP-cookies made from different formulations were determined along with control cookie and white bread as reference. The best formulation that corresponds to a wheat flour:RRSP ratio of 15:85 was found to possess a lower glycemic index of 60.53 when compared with the control cookies (77.62) based on the prediction of hydrolysis index (HI). The hydrolysis curve is shown in Figure 7, while the hydrolysis index (HI) and predicted glycemic index (GI) of the products is shown in Table 3.

Figure 7. Average hydrolysis curves of: RSRP*-cookie (), control cookie (), white bread used as reference () (Saguiln, et al., 2007).

Table 3. Hydrolysis index (HI) and predicted glycemic index (pGI) of cookies with diverse resistant starch-rich powder levels (RSRP).

Source: Saguiln, et al. (2007)

In conclusion, the usage of resistant starch-rich powder (RSRP) from banana starch can produced a bakery product with moderate available starch and slow release of carbohydrate features. The use of nutraceutical ingredients, such as RSRPs, may be useful in the development of new products for consumers sectors with reduced caloric and glycemic requirements (Abbas, et al., 2010).

3.7.2.2. Resistant Starch MuffinBaixauli, et al. (2008) studied the effect of replacing wheat flour with resistant starch on the quality of muffins. The volume, height and the number and area of gas cells in the muffins were decreased when resistant starch was used. Viscosity and the elastic properties of the muffin batter decreased as the flour was increased. Replacement by more than 10% resistant starch contributed to the decrease in the structural elements provided by wheat flour. Based on baking performance of the final baked products it was suggested that incorporation of extra ingredients that could raise the protein level into the formula, are likely to increase the elastic properties of the muffin batter during the heating process in the presence of high resistant starch (Abbas, et al., 2010).

CHAPTER IVCONCLUSION

The modified starch has many advantages compared with natural starch. Modified starches have such properties more resistant to heating, acidification and stirring, and affect the characteristics during gelatinization process. Banana starch can be modified to be resistant starch (RS) which has a lot of benefits for human health, especially as prebiotics and prevent various diseases, and and can be used as a raw material for functional food. Banana which has a high content of RS is an unripe banana.Modification of starch can be done chemically and physically. From the various methods of modification of starch, there are four of the most suitable methods to modify banana starch: the addition of acid, enzymatic hydrolysis, crosslinking (chemistry), and autoclaving-cooling (physical). Swelling power of RS is low when compared with cassava starch, so the products are made from resistant starch is not going to swell, but the health benefits are high. In the food industry, RS can be served as a texture enhancer and to make food products with high nutritional demands or low calorie. Banana resistant starch can be processed into some food products, such as crispy snacks, slow digestible cookies and muffin.

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