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Application of Starch and Starch-Based Products in Food Industry

Article  in  Journal of Science and Technology · February 2018


DOI: 10.30880/jst.2018.10.02.023

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

Application of Starch and Starch-Based Products in Food Industry


Nurulain Syuhada Mohamad Yazid, Norazlin Abdullah*, Norhayati Muhammad and Hazel
Monica Matias-Peralta

Department of Technology and Natural Resources, Faculty of Applied Sciences and Technology, Universiti Tun
Hussein Onn Malaysia, Pagoh Educational Hub, 84600 Pagoh, Johor, Malaysia.

Received 30 September 2017; accepted 16 May 2018; available online 1 August 2018

Abstract: Starch is an edible polymer derived from plant basis. It is commonly used in food industry as it
offers good stabilising effect. Moreover, starch can be easily modified either physically or chemically
making it a very versatile source. For instance, its capability to be easily modified and coming from low
cost source making starch as one of the most important ingredient in food preparation. There are currently
varieties of commercially modified starch available in Malaysian market. For example, potato, corn, wheat
and tapioca starch are presently on the top list. However, there are also numbers of unexplored native starch
for example from fruits processing waste. Besides, these fruit by-products are considered as underutilised
source of starch. Although there are few existing reported studies on starch extracted from fruits seed and
other waste products, more new sources are believed to be explored in future according to particular starch-
based products industries and demands. Therefore, this review discusses current starch based-products
developments and application of unconventional starch in food industry.

Keyword: Food Industry; Modified Starch; Physicochemical Properties; Starch; Waste.

1. Starch several selected types of food crops including


barley, corn, wheat, potato, rice and tapioca
Starch, which is the most plentiful containing starch will be described in the
carbohydrate stored in a plant acts as the key following paragraphs.
factor in determining quality of food products Barley (Hordeum vulgare L.) is a good
[1]. Moreover, it is one of the most important source of gluten-free flour producing bread
polymers that has been extensively used daily with a more compact texture as compared to
in both food and non-food application [2]. It is bread made up of wheat flour containing
normally derived from natural source of gluten [9]. Furthermore, malt and beer
polymer, available in abundance, low cost and production is depending on barley produced as
usually consumable and edible by animal or its main raw material, while it is also used for
any living creature [3]. According to [4], animal feed [10]. Livestock energy, human gut
various functions of most studied biopolymers health and fermentable sugars in brewing are
which are starch basically due to its easily depending on the degraded functional
available. Koko Krunch is an example of properties of barley [11]. It has been found by
Malaysian most common consumed cereal previous study that by substituting wheat with
grains by kids or even adults in conjunction barley bran, capability of dough water
with a study reported that the main source of absorption was increased up to 71.5% in
energy is coming from starch present in cereal chapatti production [12].
grains [5]. Moreover, it comes from a variety There are differences between a normal
of source worldwide such as barley, corn, and naked barley or known as hull-less barley
potato, wheat, tapioca and rice [6]. which commonly consumed by Tibetan people
Corn, potato, rice, tapioca and wheat are in Tibetan Plateau. Naked barley easily had
the main available source of commercially undergone threshing process. Threshing is
produced starches in the market [7]. These five known as a process of separating seeds from
starches have been categorised as gluten-free its husks or hulls [13]. During retrogradation,
starch which suits well for people with barley containing longer chains of amylopectin
allergen towards gluten [8]. Hence, making performs more perfect crystals and a higher
starch as a major raw material for food peak temperature (Tp) achieved when it has
industrial purpose. A brief explanation on been analysed by using differential scanning

*Corresponding author: norazlinh@uthm.edu.my


2018 UTHM Publisher. All right reserved.
e-ISSN: 2600-7924/penerbit.uthm.edu.my/ojs/index.php/jst
Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

calorimetry (DSC) [14]. Thus, it supports that the wheat bran has been disposed as
claim made by recent study that barley is animal feedstock despite of its rich-antioxidant
currently on number four of most consumed properties [27].
cereal crop worldwide [15]. Potatoes are produced mostly in a mild
Corn starch is as important as any other climate area whereas harvested products will
starch in industrial use. Starch isolated from be collected upon reaching autumn season
corn was fused into many baked goods such as [28]. Despite of its well played role in food
cookies, cakes, icings and fillings due to its industry, potato starch was also found to
ability in maintaining moisture content, function well in paper and textile sizing
prevent growth of crystal from sugars and together with stiffening laundered fabrics [29].
enhanced juiciness [16]. Corn starch also Recent study reported that phosphorous which
provides consistency and good gelling was found in starch of potato at a peak amount
properties during heating of corn-banana may affect functionality of this particular
custard paste [17]. Furthermore, 25% of starch [30]. According to [31], potato starch
amylose was reported present in normal corn does not respond well to pressure-induced
starch granule [18]. [19] reported that 50% gelatinization. In general, gelatinization is a
from total starch production has been utilised process occurring in the presence of water and
by food industry. According to [20], costs heat. Even though potato is the most consumed
could be saved and at the same time cow’s food crop worldwide, it has been labelled as
dairy produced could be maintained by contains a high glycaemic index (GI) due to its
supplying cow with low-corn starch based ability in causing sharp increase of blood
diets. By partially substituting wheat flour glucose level [32]. Starch produced from
with corn resistant starch, a whiter, less tapioca and potato have been extensively
yellowish and reddish cake was produced [21]. applied by both food and non-food industries
Another fun fact of corn is that in industries, it [33]. Therefore, potato is also crucial in food
comes in two varieties which is normal corn industry for starch production.
starch and the other one is waxy corn starch. Rice (Oryza sativa L.) starch which is
The composition of amylose and amylopectin made up of majority 70 – 80% of branched
varies depending on starch origin. Amylose amylopectin and 20 – 30% of linear amylose,
present in a starch molecule in the range of 20 is normally eaten in the form of cooked rice
– 30%. Whereas, highly branched glucose [34]. In Maluku, Indonesia, rice production per
polymer present at about 70% in a starch annum can only fulfil about 40% of
molecule known as amylopectin. This is consumer’s demand. Starch presence in rice
specifically for normal starch. However, the cause it one of the most utmost food crops
situation changes for waxy starch when the consumed in Asian countries like Malaysia,
composition is 100% amylopectin [22]. Indonesia and Thailand [35]. Recent study
Wheat, which is scientifically known as stated that food and non-food industries are
(Triticum aestivum) has been the oldest and enjoying benefits obtained from versatility of
most consumed crop in various forms of food rice starches [36]. Different region produced
products worldwide such as cake, cookies and different taste and variety of rice. As an
bread due to its promising energy supplies and example, there are two most common
other good constituents [23]. Baking quality of consumed rice varieties known as Basmathi
wheat products such as cookies and bread are and Irri in Pakistan. Even in Malaysia, people
depending on the starch molecular structure are common with Basmathi rice type imported
and its properties [24]. Lipids, protein and from Pakistan due to its promising aroma and
starch are main component of wheat flour [25]. quality. This is supported by a recent study,
Despite of being world’s leading food which found that the Basmathi rice is pricier
component, high consumption of wheat-based but contains more aromas whereas Irri rice is a
product can result in a negative health impact way cheaper due to its non-aromatic properties
such as obesity and type 2 diabetes [26]. In [37]. It can be concluded that rice is staple
Malaysia, bran and wheat germ bread food for Southeast region.
produced by Gardenia brand is an example of Tapioca (Manihot esculenta Crantz) has
how wheat by products have been utilised by been processed into sago and starch which
food industry which accounted 10% from the could be found abundantly in Tamil Nadu,
cereal waste production. Recent study claimed India [38]. Besides, it is a good source of

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

starch in forming soft and transparent gel utilised the goodness of starch functions and
despite of its low protein content [39]. Sour not only applicable in food industry such as in
starch produced from cassava starch can be cosmetics, textile, paper and pharmaceutical
used in bread-making and pastry production or industry [54]. On the other hand, cooking,
as an alternative for gluten-free bread [40]. processing, organoleptic capabilities and
This is consistent with previous research, starchy food digestibility are all influenced by
which claimed that rice, potato and tapioca amylose to amylopectin ratio [55]. In a recent
starch as the most leading used starches in the study reported that when comparing between
production of many gluten-free products in amylose-rich starch and amylopectin-rich
terms of texture characteristics [41]. Recent starch in terms of expanding in size,
study stated that tapioca can grow well in low amylopectin-rich starch did way better [56].
rainfall areas and barren soil thus making it an Therefore, starch structural and functional
attractive source of starch [42]. In many food properties depend solely on content and
products, thickening and gelling properties structure of amylose and amylopectin [57].
were supplied by tapioca starch [43]. There are Table 1 [58] elaborates amylose and
few benefits of tapioca starch for example amylopectin in starch.
contains no smell, clarity of paste and
stickiness which is favourable in food industry Table 1 Amylose and amylopectin in starch.
[44]. Therefore, tapioca or cassava is also as [58]
essential as other source of food crops.
Amylose Amylopectin
Starch is actually an insoluble
Linear polymer Branched polymer
carbohydrate, which composed of α-glucose
α-1,4-glycosidic α-1,4- and α-1,6-
polymers [45]. There are two most essential
linkages glycosidic linkages
components present in starch compound which
are amylose and amylopectin. These two
major polysaccharides present in starch Photosynthesis plays important roles in
supports the characteristics of biodegradable synthesising glucose molecules in plant cells.
and thermoplastic polymer [46]. In a chain of Higher photosynthetic rate produces greater
glucose polymers, there are bonds that joining yield productions. Starch is carbohydrate end
them, which are α-1,4- and α-1,6-glycosidic product obtained from plants when they
linkages [47]. According to [11], it is way perform photosynthesis and each plant have
much easier to hydrolyse starches with α-1,4- different starch distribution amount depending
glycosidic bonds than α-1,6-glycosidic bonds. on its species [59]. On the other hand, fruits
Amylase is the most important enzyme in are undeniably containing all the goodness of
catalysing α-1,4-glycosidic bonds in a starch antioxidants and helps in maintaining one’s
polymer [48]. health and weight management. Nutritionist
Low molecular weight with several long and dietician will always advise a client under
branches belongs to amylose, whereas a vast their consultation to consume more fruits due
number of short branches and highly branched to its promising health benefits. However,
polymers belong to amylopectin [49]. recent study on several commonly consumed
Moreover, within the starch granule, amylose tropical fruits in Nigeria claimed that for
and amylopectin are found in the form of people with type 2 diabetes may not suggested
water soluble lamellae and semi-crystalline to have high intake of fruits due to starch
structure [50]. Normally in starch harvested presence in that particular fruit [60].
products, amylose was found to be 20 – 30%, Starch will be less functional if it is in its
while amylopectin 70 – 80% and this amylose native conditions despite of its sources and
to amylopectin ratio are crucial in determining origins. This is supported by previous study,
each different starch physicochemical which stated few disadvantages of native
properties [51]. starch such as sensitive towards pH, low
Biological genetics backgrounds of a clarity of starch paste, high retrogradation, low
starch source have a great influence in amylose in syneresis and decomposition [61]. Besides,
and amylopectin ratio [52]. Starch derived starch presence in banana is good for human’s
from carbohydrates has a wide range of blood glucose control as resistant starch in
functions in variety of food products [53]. In banana preventing one’s blood glucose level to
addition, many different industries have have rapid increase. However, if banana starch

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

applied in industry requiring this particular On the other hand, native starch extracted
starch to swell properly, forming gel and hold from tapioca may be potentially applied as a
moisture, it will not be able to do so in its raw new thickener for fruit fillings [73]. According
conditions and yet modification still in need to [74], food industries consider well on
fulfilling such demands [62]. Therefore, next physical, chemical, physicochemical, pasting
section will be discussing on application of and thermal properties of tapioca flour and
starch in food industry and modification of starch. The versatility of starch is not only
starch. applicable to the food industry, but also in
pharmaceutical use. Starch extracted from
2. Application of Starch water chestnut fruits and pine tree seed or also
known as pinhão were tested for their ability to
Starch is the main source of energy in the act as excipients or drug delivery [75, 76].
human diet. Due to its practicality in diverse Other than that, starch is crucial in edible film
application of food products, starch is gaining production. For example, rice husk fibre starch
biggest attention as compared to other was used to produce film [77]. In another case
carbohydrate polymers [63]. Breakfast cereals, where modified corn starch films were used to
bread, cookies, pasta, pastries and noodles are coat Red Crimson grapes making longer-
among commonly processed cereal grains lasting of products freshness [78]. On the other
[64]. These are among the most common hand, starch also provides substitution towards
starch containing products available in Malaysian oil and gas sector. According to a
Malaysia. On the other hand, appearance, study reported by [79], bioethanol extracted
grade and shape of foods depending on starch from Sri Kanji 1 cassava starch is way much
viscosity attributes, retrogradation and pasting cheaper as compared to gasoline fuel. Starch
elements making starch as the main functional also helps in enhancing paper coating industry
components in food products [65]. Ability of [80, 81]. Thus, starch is necessary for food,
starch in nature to react with itself or other pharmaceutical, edible film, bioethanol
compounds leads to several usage in food products and paper coating industry.
systems such as thickener, gelling agent, Table 2 shows commercially available
stabilizing agent or as filler [66]. starch and its functions reported by previous
Normally, it can be found in the plants, studies between 2012 and 2017. Corn, wheat,
where carbohydrate store starch in the amplest potato, tapioca/cassava and rice are among the
amount. According to the Malaysian Food most commonly starch available in the market.
Pyramid, as prescribed by Ministry of Health Normally starches are added for enhancing
Malaysia, the base part of the pyramid is made quality of products in food industries. For
up of carbohydrate food sources such as bread, example, corn starch helps in increasing fibre
cereals, and rice [67]. Therefore, starches content in cake productions [82]. It also helps
based food products provide 50 – 55% of the in reducing sponge cake texture as compared
total daily energy of a human being. to wheat flour [83]. [84] reported that corn has
Moreover, starch is also significant in been extensively used for syrup production
providing energy for animal feed and especially high fructose corn syrup for
feedstock. In the food industry, starch is an industrial needs. Corn is also a good source of
essential food additive due to its gel-forming starch for thickening agent in infant formula
ability, thickening agent and stabilising food [85].
products [68, 69]. A study was done to help Wheat starch, on the other hand, has been
people with dysphagia, which is difficulty in used in breadfruit cookies formulation [86]. It
swallowing starch-based products, by was also found to supply gelling properties to
modifying food consistency using sago and food products [87]. Potato starch was found to
tapioca starch that acts as thickener [70]. act as a good pasting and gelling agent at the
Different starches source fulfilling various same time [88]. Potato starch film was also
industrial demands. As an example, sago found be able to be produced from potato
starch is great in terms of elasticity, softness, starch [89]. Tapioca/cassava starch was
flexible to use and less adhesive [71]. As reported in a previous study to help in risen up
compared to tapioca starch that has a very the quality of jasmine rice bread gluten-free
cohesive texture despite of its better cold quality [90]. Besides, tapioca starch is also a
stability [72]. good thickening agent in fruit filling

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

production such as blueberry filling in a improve gelling properties when added with
blueberry cheesecake [91]. In addition, it was hydrocolloids such as sodium
also found to increase the quality of soup carboxymethylcellulose (CMC) and hydroxyl-
production [92]. Last but not least, rice starch propyl methylcellulose (HPMC) [94].
acts as an emulsion stabiliser [93] and able to

Table 2 Commercially available starch and functions.


Starch source Function
Corn Increased fibre content in cake production [82].
Reduce sponge cake texture as compared to wheat flour [83].
Corn syrup production [84].
Thickener in infant formula [85].
Wheat Breadfruit cookies formulation [86].
Gelling properties [87].
Potato Pasting and gelling properties [88].
Production of potato starch film [89].
Tapioca/ Cassava Increased quality gluten-free jasmine rice bread [90].
Thickener in fruit filling [91].
Enhancing soup product [92].
Rice Emulsion stabiliser [93].
Improved gel properties with the addition of hydrocolloids [94].

Recent study reported that the knowledge offers multiple functions in food and non-food
of pasting properties in starch-based products industry [102]. Hairless Canary Seed (Phalaris
is important in order to get required Canariensis L.) and jackfruit seed were
consistency [95]. Viscosity, gelling, reported to act as a good gel stabiliser [103,
digestibility and stability of frozen storage of 104]. Quinoa, on the other hand, is extremely
heated starch suspensions were all depending stable and widely used in food grade pickering
on the starch chemical and structural emulsion stabiliser specifically in (particle-
characteristics together with different origins stabilised emulsion) [105]. Carob is an
and botanical source [96]. Starch is the most excellent source for making gluten-free bread
important edible polysaccharide containing which suits people that are gluten intolerance
nutritionally high to low molecular weight [106]. Sweet potato, on the other hand, has
sugars [97]. Food industry uses starch as a been widely used in Chinese starch industry
thickening, bulking agent, gelling and for [107]. Another example is Chestnut (Castanea
water holding capacity making it as a treasured sativa Mill) which was claimed to have the
factor [98]. Recent study documented that same function as corn starch but when
fully digested starch in small intestine is extracted by using low processing temperature
known as digestible starch, the incompletely [108]. Pinhão helps in β-carotene
digested starch in small intestine is known as microencapsulation [109]. Jackfruit which is
partially digested starch, while starch that common to Southeast Asia and India was
totally forbids digestion in small intestine is found to have seeds that able in increasing
known as resistant starch [99]. Table 3 shows quality of chocolate aroma produced [110] and
a list of underutilised starch and its functions for encapsulation process of rice bran oil
documented by previous studies. Underutilised [111].
source of plants remain undiscovered despite In addition, seeds of these Artocarpus
of its contribution to rising of world’s food genus were reported to function well in
production [100]. gelatinisation properties [112]. Flour was also
Food industry favours starch which is one of the most common thing that can be
stable, white in colour and odourless thus obtained from jackfruit seed [113]. Thus, the
making (Araucaria angustifolia) seed as a jackfruit seed flour has ability of producing
perfect candidate by having 34% starch [101]. reduced calorie chocolate cake [113].
Recent study claimed that it is crucial to Mangifera Indica kernel, on the other hand,
explore new and underutilised starch as it was documented in two previous studies to

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

function well as a coating agent. In the first to 95 °C [120]. The unripe banana was found
study, it was found to coat the almond kernel to have high ability in forming pasting
[114]. Starch extracted from mango seeds properties [121]. Whereas, in another study
shows a superficial amount of starch which comparing cooking banana and dessert banana,
can be utilised in industry needing starch both have claimed to own potential in acting as
[114]. In the second study has reported that the an emulsifying agent [122]. Recent study
mango kernel starch could help in retaining a stated that pea (Pea sativum) and Bambara
longer shelf life of a tomato (Solanum groundnut (Vigna subterranea) is an
lycopersicum) fruit [115]. From industrial by- underutilised food crops in Nigeria and
products, mango kernel can be easily obtained currently explored of its potential in terms of
and produced at low cost [116]. starch isolation [123]. Lastly, litchi or is also
Besides that, soursop (Anona muricata) known by Malaysian as lychee can be obtained
starch extracted from its white fleshy flesh has in fresh form or canned in glucose syrup. Its
been used in bread production [117]. Tikhur kernel starch was reported to have good gel
(Curcuma angustifolia) was found to be able strength and elasticity [124]. Starch extracted
in having properties as tapioca sago starch from underutilised sources has numbers of
[118], while moth bean (Vigna Aconotifolia) unexploited applications. Therefore, it is
was claimed to be having good quality for important to do further research on potential
food products requiring high thermal stability source of starch either from indigenous fruits
[119]. On the other hand, tamarind or in or botanical source, or it could be from
Malaysia is widely known as ‘asam jawa’ was industrial processing waste such as fruit peels
reported by recent study that it contains high and seeds.
swelling power when tested in the range of 55

Table 3 Underutilised starch and functions.


Starch source Function
Hairless Canary Seed Gel stabiliser [103, 104].
(Phalaris Canariensis L.)
Quinoa Food grade pickering emulsions stabiliser
(particle-stabilised emulsions) [105].
Carob Gluten-free bread production [106].
Sweet potato Used in Chinese starch industry [107].
Chesnut (Castanea sativa Mill) Substitute to cornstarch - lower processing temperature [108].
Pinhão Microencapsulation of β- carotene [109].
Jackfruit seed Chocolate aroma production [110].
Rice bran oil encapsulation [111].
Gelatinisation purposes [112].
Flour production [113].
Production of reduced calorie chocolate cake [113].
Mango kernel Coating purpose – almonds (Prunus dulcis) kernels [114].
Edible coating for enhancing shelf- life of tomato (Solanum
lycopersicum) fruit [115].
Composite film production [116].
Soursop (Anona muricata) Bread production [117].
Tikhur (Curcuma angustifolia) Mimic properties of Tapioca Sago [118].
Moth bean (Vigna Aconitifolia) For food products requiring high thermal stability [119].
Tamarind (Tamarindus indica L.) For food products requiring high swelling power [120].
kernel starch
Banana For food products requiring high pasting ability [121].
Emulsifying agent [122].
Litchi kernel starch Good gel strength and elasticity [124].

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Journal of Science and Technology, Vol. 10 No. 2 (2018) p. 144-174

3. Starch Modification starch by using ether agents resulted in


amphiphilic side chains of product and
Starch is found in an ample amount and hydrophobic character of starch modified
fall into second place compared to other product was fixed by the length of alkenyl
carbohydrates and by applying some groups [139]. Recent study on using
modification it can fit to various industrial chemically modified starch in replacing fat in
demands [125]. Starch has broad applications yogurt based products, suggested a good effect
in food industries. However, starch in native in syneresis and good flow and better
state is unable to attain specific industrial viscoelastic characteristics [140]. However,
requirement. Thus, modifications can be made there are two major disadvantages of utilizing
either physically or chemically [126]. In order solely pure starch which first is high attraction
to improve starch pasting properties and shelf towards water and second is extreme rigidity
life extension, modification of starch by using [141].
chemical is the most frequently used method Moreover, chemically modified starch will
[127]. Processing quality can be improved by be susceptible to amylolytic enzymes due to
altering pasting, gelatinizing and the presence of chemical substituents and
retrogradation properties of starch [128]. additional bonds [142]. Maltodextrin is an
Commercialized starch such as corn and other example of enzymatically modified starch by
type of cereals are normally underwent using amylolytic enzymes [143]. An adequate
physical modification or simple chemical amount of starch-stearic acid complexes can
modification to enable them to be used by food be formed by modifying pure starch using few
or other industry [129]. Starch was modified methods such as acetylation, de-branching and
physically or chemically in order to obtain using enzyme such as β-amylase [144].
heat stable or resistance towards heat product, Canned and frozen foods required starch with
stable during freeze-thaw process and easily low viscosity, thus starch modification is
dissolve either in hot or cold suspension [130]. crucial in order to get the required viscosity
One of the most common modification [145]. Modification of starch helps in
methods by using chemical is crosslinking enhancing industrial application. One of them
[131]. Introducing intra and intermolecular is pharmaceutical. Modifying corn, cassava
bonds in starch molecule at random locations and sweet potato using acetylation helps in
is known as cross-linking [132]. Thermal producing stronger paracetamol which is not
properties of starch can also be modified by easily crumble during transportation and
applying cross-linking agent and not only storage until reaching consumer [146].
changing physical characteristics however this Table 4 and Table 5 show some of the
is all depending on starch plant origin and chemical and physical method for starch
botanical source [133]. Moreover, starch that modification done by previous studies. Table 4
has undergone chemical modifications is shows examples of starch that has been
extensively used in food industry due to its chemically modified. According to [147],
better emulsion and pasting characteristics oxidation produces starch film with the most
[134]. Native starch which is modified using stable tensile strength. Cross-linking and
acetylation and oxidation may be used as food oxidation of starch isolated from elephant foot
additives [135]. The disadvantages of using yam (Amorphophallus paeoniifolius) help in
chemical modification are easily causing improving paste clarity, solubility and thermal
chemical residue to be left after modifying characteristics when tested using DSC without
starch and definitely not an eco-friendly even causing any effect on starch granules [148].
though it is a fast, simple, extensively used and Starch with low paste viscosity is suitable
efficient method [136]. for production of edible coatings and
Chemical modification of starch usually biodegradable films [149]. Maleic acid was
involves acid or base at high concentration to used to modify jackfruit seed starch in India to
destroy hydrogen bond intermolecular produce starch with high solubility because
interactions and crystallization areas [137]. acid tends to break down the amylopectin at
Hydroxyl group presence in starch may cause 1,6 bonds [150]. On the other hand, ionic
chemical reaction by exposing one or more gums were used in a study of modifying water
reactive groups on its surface and will be chestnut (Trapa natans) starch [151].
efficiently coupled to matrix [138]. Modifying

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Table 4 Chemically modified starch.


Starch source Modification
Lotus rhizome (Nelumbo nucifera) Oxidation and cross-linked [149]
Elephant foot yam Oxidation and cross-linked [148].
(Amorphophallus paeoniifolius)
Jackfruit seeds Maleic acid [150]
(Artocarpus heterophyllus Lam)
Water chestnut (Trapa natans) Ionic gums [151]
Tapioca Acetylation [152]
Acetylation – acetic anhydride [153]
Esterification – Dodecenyl succinic anhydride [154]
Maize Acetylated (Ac) [156]
Cross-linked [157]
Acha (Digitaria exilis) Cross-linked with citric acid [158]
Banana (green/unripe) Hydrochloric acid [159]
Mango kernel (Mangifera indica L.) Hydrochloric acid [160]
Rice (Oryza sativa L.) Citric acid, lactic acid and acetic acid [161]
Acetylation – acetic anhydride [162, 163]
Cross linking – citric acid [166]
Sago Acid hydrolysis and hydroxypropylation [167]
Acetylation – acetic anhydride [168]
Esterification - Octenyl succinic anhydride (OSA) [169]
Durian (Durio zibethinus) seed starch Acetic acid [170]
Cross-linking [171]
Avocado (Persea americana, Miller) Acetic acid [172]
Cross-linking [173]
Black eyed pea (Vigna unguiculata) Acid hydrolysis – Concentrated hydrochloric acid (36%
by weight) [174]
Carioca beans Oxidation – sodium hypochlorite [175]
(Phaseolus vulgaris L.; cv. Pérola)
White Sorghum (Sorghum bicolor) Oxidation – sodium hypochlorite [176]
Dual modification – acid hydrolysis and succinylation
[177]
Potato (Solanum tuberosum L.) Oxidation – sodium hypochlorite [178]
Acetylation and oxidation [179]
Oxidation [180]
Cross-linked with acetic anhydride [181]
Cross-linked with sodium trimetaphosphate (STMP) /
sodium tripolyphosphate (STPP) [183]
Barley (Hordeum vulgare) Acetylation – sodium hydroxide (NaOH) and oxidation
(active chlorine) [184]
Yellow sorghum Acetylation, benzylation and hydroxypropylation [185]
Red Zaragoza bean (Phaseoluslunatus) Acetylation – acetic anhydride [187]
seeds
Pinhão (Araucaria angustifolia) seeds Acid hydrolysis – hydrochloric acid [188]
Musa AAB (Poovan banana) Acetylation [190]

Tapioca starch has been used as an Chlorogenic acid (5-caffeoylquinic acid,


alternative source for products requiring CGA) was claimed to aid in sliming process
encapsulation as it comes from inexpensive and could be found in a plentiful amount
source and in this case it helps to slow down present in green coffee beans mainly Robusta
release of crucial bioactive compound such as species [153].
chlorogenic acid due to its increasing in Acetylation is a chemical modification
hydrophobicity after acetylation [152]. process by introducing acetyl groups in starch

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chains and this process can be confirmed by whiter and more opaque when compared with
Fourier transform infrared spectroscopy non-glutinous or non-waxy rice [165]. Native
(FTIR) [154]. Recent study suggested that by rice starch is extensively used as binding agent
adding acetyl groups to cassava starch, it and thickener in sauce production, puddings,
enables to be part of stabiliser in emulsion and foods for baby and processed meats. However
starch gel in frozen food products as it can when modified using cross linking agent such
function well at low temperature [155]. as citric acid, result obtained showed a better
Besides, maize or corn starch was also application of rice starch in food industry as a
modified using the same acetylated (Ac) dietary fibre [166].
method and cross-linked [156, 157]. Cross- By combining acid hydrolysis and
linking of starch was reported in a study on hydroxypropylation, modified sago starch are
acha (Digitaria exilis) starch by introducing less prone towards retrogradation and even at
citric acid [158]. high concentration it is still able to solubilise
Modified unripe banana using in cold water [167]. On the other hand, sago
hydrochloric acid does not show any changes starch in Papua has been modified using acetic
based on its pattern which has been proved by anhydride in acetylation process in order to
X-ray diffraction and based on its structure by improve its thickening properties [168].
scanning electron micrograph [159]. Structure Esterification is one of the modifications listed
and shape of starch granule isolated from under chemical modification. Modification of
mango kernel (Mangifera indica L.) and has native sago starch using esterification process
been modified by using acid also do not show using octenyl succinic anhydride (OSA) cause
any changes [160]. it to have potential to be applied as thickener
Rice (Oryza sativa L.) was previously replacing Arabic gum, emulsifier and oil-water
modified by using three types of organic acids emulsion stabilizer [169].
which are lactic, citric and acetic acid. The Durian seed starch obtained from night
citric acid has the best result in modifying rice market in Perlis and Kedah, Malaysia was
starch as it increases starch solubility [161]. modified by using acetic acid in realising idea
By inserting acetyl groups into native starch, it of using durian waste in order to be an
will cause amylose and amylopectin to alternative source of starch replacing current
reassociate its current order and leads to dependence on petroleum-based plastics [170].
decreasing in gelatinization temperature. This Starch extracted from durian seed not only
is where the process will be beneficial to applicable for food industry. Recent study
industry when acetylation helps in reducing reported that modified starch by cross-linking
temperature for starch to gelatinize and will from durian seed was found to act as a natural
cut industrial processing cost. Acetylation flocculant in landfill sector as the modification
causes starch granules in low-amylose rice treatment helps in improving starch
starch to breakdown in which producing end interconnection [171].
products containing relative stability during Modification of starch by using lactic acid
cooking and sensitive to high temperature shows no changes in structure of avocado seed
[163]. when analysed by using scanning electron
In order to classify starch, there are two micrograph (SEM) while it causes reduction in
common classifications which are waxy and thermal stability and crystallinity [172]. In a
non-waxy starches. Waxy starch is made up of recent study, modifying avocado seed starch
100% amylopectin with low amylose or either was done by using cross-linking method
contains no amylose, whereas non-waxy starch (Persea americana Mill.). Results obtained
has 20 – 30% amylose and 70% amylopectin. suggested that starch isolated from avocado
Rheological and textural properties of waxy seed can be an alternative source towards
rice products depend on its structure and current available commercial starch source as
gelatinization temperature [164]. Previous it helps in improving paste viscosity and
study comparing two rice starch varieties stability for cream soup production. In
available in Australia claimed that waxy rice addition, chain of starch is stronger than native
or commonly known as glutinous rice starch starch due to the presence of phosphate group
loses its original shape when heat is applied gained during cross-linking process [173].
due to the presence of air space between the By applying concentrated hydrochloric
starch granule. Besides, its endosperm is acid at 36% by weight, black eyed peas (Vigna

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unguiculata) starch was able to be modified using cross-linking agent for example acetic
successfully when it shows an increment in its anhydride which in turns resulting in starch
solubility, freeze-thaw stability and clarity of product that has high resistant towards heat,
paste [174]. Common bean starch was acid and increase in shearing properties as
modified by oxidation process using sodium compared to native and unmodified starch
hypochlorite as oxidizing agent. Results [182]. Another study reported modifying
obtained proposed that these modified starch potato starch using sodium trimetaphosphate
might be an alternative source in coating food (STMP) or sodium tripolyphosphate (STPP) as
products and in dairy products. In addition, as its cross-linking agent resulted in modified
the concentration of oxidizing agent increases, starch having desired properties to be applied
starch obtained shows whiter in colour which in food industry such as binding agent,
could be a substitute in paper manufacturing stabilizer and thickener [183].
[175]. Previous study found that by inserting
Previous study suggested that oxidation acetyl group through acetylation and addition
helps in improving solubility and paste clarity of carbonyl and carboxyl group by oxidation
of white sorghum starch and could be an makes barley starch decreasing in its viscosity
alternative source for food products requiring and in turns reducing possibility to retrograde
high solid contents without over-thickening which could be a potential source in making
[176]. Reported studies claimed that white biodegradable films [184]. Yellow sorghum
sorghum starch modified by combined acid starch was subjected to acetylation,
hydrolysis and succinylation resulting in lower benzylation and hydroxypropylation resulting
paste viscosity, less gumminess and reduced in in food product having low tendency towards
tendency towards retrogradation which suits in retrogradation which could be a good
food products requiring these properties for alternative source in sauces and bread
example frozen pie filling, custards and production [185].
puddings [177]. During heating of starch in excess
Several studies have suggested acetylation availability of water, starch takes up water and
and oxidation mode of modification makes swelling occur inside the granule. In this
potato as a potential source of film which can condition, amylose and amylopectin disappear.
withstand high water activity in its This is called as gelatinization process. When
surrounding. First study claimed that oxidation heating stops, amylose starts to form back and
using sodium hypochlorite caused potato in a longer term amylopectin will follow the
starch to have low water solubility as same condition. This is known as
compared to its native starch. This study retrogradation [186]. Increasing degree of
suggested modified potato starch can be turned acetylation in zaragoza (Phaseoluslunatus)
into film and use it in a higher water activity bean seeds starch obtained from Colombia
environment [178]. resulting in a good alternative source in cream
Oxidation of potato starch as reported in manufacturing due to high viscosity level
previous study using oxidizing agent caused [187].
hydroxyl group of starch to transform into Modification of pinhão seed starch using
carboxyl or carbonyl group which could be hydrochloric acid shows end result having
one of the reason increasing in hydrophobicity better solubility and more transparent which
of modified potato starch [179]. Second study could be an alternative source in coating
reported potato starch modified using materials or film [188]. What is actually
acetylation shows greater reduction in water happening during hydrolysis of acid is acid for
vapour absorbing capability as compared to example hydrochloric acid was added to the
modification using oxidation process [180]. suspension of starch in aqueous condition and
Potato starch properties were reported unable controlled at certain desired temperature below
to modify most efficient at temperature of gelatinization temperature for a fixed period of
25°C or lower when using acid hydrolysis time [189]. Results obtained from this study
[181]. reported that pasting properties of poovan
On the other hand, cross-linking suggested banana from India rises after acetylation
different methods of modification in potato process compared to its native form [190].
starch. Present hydrogen bonds in potato Table 5 shows several examples on
starch will be strengthen during cross-linking physically modified starch. Altering starch

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granules and molecular structure is practiced retrogradation and enhancing in paste and gel
in physical modification of starch in order to properties when in use [191].
obtain a stabilize starch granules, decreasing in

Table 5 Physically modified starch


Starch source Modification
Corn Ultrasound treatment [211]
Heat moisture treatment [212]
Pinhão (Araucaria angustifolia) Annealing, heat-moisture, sonication [214]
seeds Ultrasound treatment [215]
Heat moisture treatment [217]
Potato Ultrasonic treatment [218, 219, 220]
Annealing and ultra - high pressure (UHP) [221]
Rice Annealing [222]
Heat-moisture treatment [223]
Improved Extrusion Cooking Technology (IECT) [224]
Parboiling – steeping step [225]
Ultrasound treatment [226]
Sweet Potato Annealing [227]
Heat-moisture treatment [239]
Repeated heat moisture treatment (RHMT) [228]
Steam explosion [229]
Wheat Annealing and ultra - high pressure (UHP) [230]
Ultrasound treatment [231]
Yam (Dioscorea spp.) Annealing [229]
Annealing and ultra - high pressure (UHP) [229]
Heat moisture treatment [232]
Jackfruit seed Microwave [233]
Partial gelatinization [234]
Foxtail millet Heat moisture treatment [235]
Ultrasound treatment (UT) [236]
Sago Heat moisture treatment [238]
Red adzuki beans Continuous and repetition heat moisture treatment [240]
Taro Microwave and heat moisture treatment [241]
Water chestnut Microwave [242]
Acorn Annealing and heat moisture treatment [243]
Lotus (Nelumbo nucifera Gaertn) Microwave [248]
seed
Tapioca Ball – milling [249]
Bambara groundnut (Vigna Annealing [254]
subterranea)
Ensete/False banana Annealing and heat moisture treatment [255]
(Ensete ventricosum Musaceae)
Morado banana Heat moisture treatment [256]
Banana (Musa sapietum and Musa Heat moisture treatment [258]
paradisiaca)
White Sorghum Annealing [259]
(Sorghum bicolor)
Arrowroot Autoclave – cooling treatment [260]
(Marantha arundinacea L)

Heat moisture treatment (HMT) helps in ultrasound is another method commonly used
improving elasticity of dough made from to modify starch physically. Recent study
wheat and barley flour [192]. Besides HMT, reported that ultrasound is gaining recognition

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due to its various benefits such as low cost, hand, starch modified by using the chemical
efficient and eco- friendly as no chemical for example sodium hypochlorite (NaOCl)
usage involved as compared to other chemical produced end products that have high
modification method [193]. According to viscosity, stronger resistance to acid, heat, and
[194], larger bubbles can be formed if lower shear, swelling decreases and not easily
frequency of ultrasound used and cavitation breakdown [206]. Starch paste properties can
process that occur during ultrasound causing be easily modified expressively by applying
both covalent and non- covalent bond inside several cross-links [207].
polymer such as starch to be broken down. By When people consuming starchy foods for
applying ultrasound, starch component present example bread and rice, main supply of energy
in plant polymer can be modified physically was actually supplied by physical and
[195]. chemical properties of starch that act as main
If modifying starch by using either fully or source of carbohydrate [208]. Increasing the
partially gelatinization, it will be able to starch paste stability and reducing pH, heat
produce starch with cold water-swelling and shear properties of tapioca starch during
capacity and gel barrier properties [196]. Rice food processing is the main focus of
(Oryza Sativa L.) being the major nutrient and modifying starch by food scientist in Thailand
calories source of Asian people was found by [209]. As an example, by undergo dual
recent study in reducing its glycaemic index modification process, sorghum starch was
by applying heat moisture treatment and reported to be a new potential source replacing
annealing [197]. The usage of modified starch current available biodegradable films [210].
among them is to increase viscosity, shelf life Corn starch was reported successfully
of food products, textures, solubility, modified by applying ultrasound treatment
appearance and emulsification of food [211]. Pre-treated samples with ultrasound
products [198]. Annealing is categorised under treatment helps in altering corn starch
hydrothermal modification method of starch physicochemical properties [212]. In another
other than HMT. The process of annealing study, corn starch was modified using heat
includes starch nurtured in an excess amount moisture treatment and resulted in reduction of
of water in a temperature range below swelling power, percent solubility,
gelatinisation temperature but higher than gelatinization enthalpy and pasting viscosities
temperature of glass transition [199]. when compared with untreated corn starch
Starch has been modified in order to gain a samples [213].
better surface area and increase in pore volume Pinhão (Araucaria angustifolia) which
due to its huge presence worldwide at low cost could be found in Brazil and was reported to
[200]. Moreover, according to [201], varieties be in high starch content and can be modified
of indigenous corn starches from different physically using process of annealing, heat-
botanical sources have been well studied and moisture treatment and sonication [214].
reported by previous researchers regarding its Physically modified pinhão seed shows better
physicochemical characteristics. Recent study results in terms of syneresis whereas other
reported that modified starch able to replace parameters show no significant difference as
current available dietary fat [201]. Human compared to its native starch [215]. Pinhão
beings and animals with simple single- seed obtained from pines trees that grow well
chambered stomach like cats, rats and pigs in forests Southern part of Latin America and
unable to digest native starch granules well when applying HMT, molecular structure and
[202]. When comparing between maltodextrin, its properties changes which suggested that it
native and modified tapioca starch, it was could be utilised as it is an underutilised
found that modified tapioca starch had a source of starch and apply in food and non –
broader distribution of particle size [203]. food based application [216]. HMT is an
Three most common function of modified example of physical modification which
starch in food industry are as agent of gelling, reported in previous study on pinhão seeds can
stabilising and thickening [204]. According to provide strongest effect towards gelatinization
[205] starch-modified physically for example and enthalpy if tested using differential
using the most common treatment such as scanning calorimeter machine [217].
heat-moisture treatment and annealing can Potato was also modified by using
produce a safe raw material. On the other ultrasound treatment [218, 219, 220]. Basically

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ultrasound is a sound waves having a chemical properties without disturbing starch


frequency which beyond human hearing structure of molecule [236]. Heat moisture
capability [221]. On the other hand, for rice treatment when combined with citric acid
starch, several methods have been reported by shows changes in sweet potato starch
previous studies. Annealing [222], HMT crystallinity type from B to C and reduced its
[223], improved extrusion cooking technology peak viscosity which shows that by applying
(IECT) [224] and ultrasound treatment [225]. such treatment, a significant change can be
Steeping is the first step in parboiling process observed. Besides, another study reported
followed by heating and drying of rice. Recent starch isolated from sweet potato starch were
study reported that starch isolated from rice successfully modified using repeated heat
kernels is different from kernel itself in terms moisture treatment (RHMT) when a
of its structure and properties [226]. Recent significant changes were observed on X-ray
study suggested starch extracted from sweet diffraction pattern and its crystallinity, thermal
potato modified by using steam explosion can and pasting properties when compared with
be a good source for treating diabetic patients native starch [237].
by encapsulating this starch into the medicine Better noodles in terms of elasticity and
[227]. Sweet potatoes were claimed by firmness were detected in noodles made up
previous research on applying annealing [228] from sago starch that has undergone heat
and HMT [229]. moisture treatment [238]. In addition, another
Recent study claimed that by annealing study also claimed that HMT caused reduction
wheat starch, stability increases as the in sweet potato starch viscosity but shows
interaction between the starch chains rising in swelling power and solubility as
increases. Combining both method of compared to native or modified starch using
annealing and HMT modification causes annealing process [239]. Reduction paste
starch granules structure in yam and potato viscosities properties, swelling power and
starches to change [231]. Yam (Dioscorea solubility is supported by another study using
spp.) starch was physically modified by continuous and repeated heat moisture
annealing process [229]. Annealing or also treatment towards red adzuki beans starch in
recognized as tempering has caused a rising in Yangling, China [240].
pasting temperature, peak time, setback and Taro starch was modified using dual
final viscosities of yam starch as compared to modification of microwave and HMT shows
modification using acid hydrolysis, results better results in terms of viscosity and freeze-
obtained is vice versa [232]. thaw stability as compared to native taro starch
Recent study in Vietnam had partially [241]. By applying microwave heating, starch
gelatinized jackfruit seed starch as a extracted from water chestnut shows
modification procedure and results showing increasing in pasting properties and enthalpy
highly soft and elastic starch gel [233]. values. However, the swelling power and
Modification of starch by using microwave percent solubility decreases [242]. Main
was found to be more efficient and time saving reason of utilising modified starch in food
compared to modification by using acid in a industry is due to its ability in rapidly
study using starch isolated from jackfruit seed dissolves in cold water [242].
in India [234]. Acorn is the fruits gained from oak tree
Previous study reported that by applying categorised under genus Quercus, which has
physical modification such as hydrothermal been modified by using annealing and HMT.
treatment, modified starch obtained will be The HMT gave more significant result in
more viscous, transparent, stable and swelling terms of altering starch properties compared to
power will also increase when compared with annealing [243]. Previous study stated that
native starch. In addition, this process is amylose and amylopectin are the main
known as pre-gelatinisation which could be the component of acorn starch though amylopectin
initial step crucial before chemical composition was found higher than amylose
modification [235]. Foxtail millet starch in [244]. In a study producing gluten free bread
previous study was reported can be modified from acorn flour, substitution at 20% shows
by using HMT and ultrasound treatment (UT). the most significant impact on volume of
Heat moisture treatment is an interesting and bread and its physical characteristics.
alternative way of modifying starch physico- However, beyond these 20% addition of acorn

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flour will reduce bread volume. In conjunction of gel, less opaque and enriches gel texture
with previous statement, carbon dioxide [253].
presence in gluten network formation inside Modification of Bambara groundnut
bread dough has been reduced due to gluten (Vigna subterranea), an underutilised starch
network deficiency which in turns resulting in source from Nigeria using annealing process
bread with lowers loaf volume [245]. reported to have caused cracks and pores on
Recent study claimed that lotus is starch surface based on image obtained from
normally found in a dried form rather than SEM [254]. In a study of modifying starch
fresh form due to its short life span in fresh using both hydrothermal treatment which are
condition which contributes by enzymatic annealing and HMT, results obtained showed
browning, microbial growth and deterioration false banana (Ensete ventricosum Musaceae)
of quality [246]. Lotus seed starch (Nelumbo starch could be possibly used as functional
nucifera Gaertn) has been modified using ingredients in both food and pharmaceuticals
microwave heating, which resulted in industry [255]. In a study of modifying
increment of its crytallinity, volume of pore Morado banana starch using HMT, results
and surface area, whereas yield of extraction gained indicated that it a good method of
and average size of starch particle decreases producing starch which could fit industrial
[247]. Another study reported using needs in terms of added value product [256].
microwave radiation on lotus seed starch helps HMT was able to change the diffraction
in producing starch with low glycaemic and patterns based on X-ray diffraction results on
hydrolysis index due to increasing in number two types of banana starch (Musa sapietum
of resistant and slowly digestible starch by and Musa paradisiaca) in Nigeria from B to C
amplifying microwave radiation [248]. type [257]. Recent study claimed that
In this study, three methods of tapioca annealing is a greener way of modifying
starch modification has been combined which desired properties of starch and enhance final
are through enzymatic, acid hydrolysis and product quality [258]. White sorghum
physical modification using ball milling as it (Sorghum bicolor) starch was subjected to
was claimed to change structure of starch from annealing in a reported study shown increasing
its native condition to smaller size of starch in paste clarity. Thus, it could be a functional
granule [249]. Tapioca starch in paste form additive in a food product requiring starch
contains no odour, high in paste clarity and with high clarity [259].
stickiness make it extensively used in food and Arrowroot is popular among Indonesian as
non-food industry in Thailand. However, like it is one of the carbohydrate sources and
other starch in native condition, tapioca starch scientifically known as (Marantha
unable to perform well in industry as it arundinacea L) has been modified using
produces unwanted characteristic of gel with autoclave and cooling treatment. Gel produced
weak structure, cannot withstand shear forces from physically modified arrowroot showed a
and reduction in stability of viscosity when softer texture and less rigid [260]. Annealing,
heat applied [250]. HMT, ultrasound and sonication are widely
In order to have a better quality of starch used in physical modification of starch.
based product, many of starch source have However, there are also other methods to
different degree of gelatinization so it can fit modify such physically such as parboiling, ball
many food formulations depending on product milling, microwave and gelatinization.
needs [251]. Recent study found that by Therefore, there are varieties of choices to
adding physically modified starch to yogurt modify starch physically.
based product containing skimmed milk
powder, it enhances consumer acceptance and Conclusion
yogurt become creamier and having consistent
texture compared to non-added starch based In conclusion, starches are widely used in
yogurt [252]. Modification of native starch food industries. Thus, modifying starch to
will not only result in reduction of fulfill specific industrial needs can be done
retrogradation occurrence but will also benefit either using chemical or physical treatment.
in many ways. For example, paste of modified Numbers of starch in the future should be
starch will be more stable during cooling and produced from unexplored source with further
freezing process, less prone towards formation studies done. This is because rather than to

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reduce the waste, it is cheaper and easily [7] Naz, M.Y., Sulaiman, S.A., Ariwahjoedi
available source. The underutilised starch B. & Shaari, K.Z.K. (2014).
should be transformed into a more useful “Characterization of Modified Tapioca
product for future use. Starch Solutions and Their Sprays for
High Temperature Coating
Acknowledgements Applications” in The Scientific World
Journal.
Authors are thankful to Universiti Tun Hussein [8] Horstmann, S.W., Belz, M.C.E.,
Onn Malaysia for providing research facilities Heitmann, M. Zannini, E. & Arendt,
and financial support through Centre for E.K. (2016). “Fundamental Study on
Graduate Studies, Short-Term Grant (UTHM- The Impact of Gluten-Free Starches on
STG-U538-2016), and Postgraduate Research The Quality of Gluten-Free Model
Grant (UTHM-GPPS-U813-2017). Breads” in Foods, Vol. 5. No. 2 pp. 30.
[9] Djurle, S., Andersson, A.A.M. &
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