Practical Report Date : Tuesday, April 25th 2019

Technology of Starch, Sugar Group : P4

and Sucrochemical Lecturer : Dr. Farah Fahma, STP.MT
Assistants :
1. Ihsan Nur Faqih F34150007
2. Deny Satriawan F34150026

PRODUCTION AND CHARACTERIZATION OF MODIFIED

STARCH

Arranged by :
Yoseph Ari Matheas F34160017
Ferry Haidir Irawan F34160069

AGROINDUSTRIAL TECHNOLOGY DEPARTMENT

FACULTY OF AGRICULTURAL TECHNOLOGY AND ENGINEERING
IPB UNIVERSITY
BOGOR
 2019
INTRODUCTION

Background

Starch is a carbohydrate which is a glucose polymer, and consists of

amylose and amylopectin (Jacobs and Delcour 1998). Starch can be obtained from
seeds, tubers, vegetables and fruits. Natural sources of starch include corn,
pumpkin, potatoes, sweet potatoes, bananas, barley, gandul, rice, sago, amaranth,
cassava, canna and sorghum. The use of native starch is still very limited because
its physical and chemical properties are not suitable for widespread use.
Therefore, starch will increase its economic value if modified its properties
through physical treatment, chemistry, or a combination of both (Liu et al 2005).
In general, starch is divided into two groups, namely native starch and
modified starch. Natural starches have deficiencies that often inhibit their
application in the food processing process, so modification of starch is needed to
cover their deficiencies. Modified starch is starch whose OH group has undergone
changes in chemical reactions (Munawaroh 1998). According to Charalambous
(1995), states that amylose and amylopectin have differences in the solubility
properties in water. Amylose is difficult to dissolve and is unstable in aqueous
solution, forming an aggregate and will undergo hardening (retrogradation) unlike
amylopectin, because the branches of the structure are more stable and less
hardened.
In food processing, starch and starch derivative products have nutritional
value and provide functional properties. Starch and its derivatives regulate or
control the beauty and organoleptic properties of some food processing processes.
The addition of modified starch or starch derivatives to food aims to facilitate the
processing, texture giving, thickening, regulating water content, consistency, and
storage stability and producing the desired appearance (Hui 1992).

Objectives

The purpose of this practice is to produce flour from modified starch from
various sources of flour and starch. The jam in producing flour and modified
starch also has the purpose of analyzing the characteristics of flour and modified
starches that have been produced and compared to existing standards.
 METHODOLOGY

Materials

Materials are used in this laboratory such as fresh cassava, dry yeast, lactic
acid bacteria, kitchen salt, starch (tapioca, sago, cornstarch), iodine solution, 95%
neutral alcohol, 0.05 N NaOH, PP indicator, 3% HCl, H2SO4 0.325N, NaOH 1 ,
25 N, 40% NaOH, Luff Schroll Solution, KI, and starch indicator.

Tools

Tools are used in this laboratory such as knife, basin, steamer, pan, stove,
dryer and grinder, cup, stirrer, flour sieve, baking sheet, blender, test plate, drop
pipette, microscope, aluminum dish, oven, porcelain cup , furnace, erlenmeyer
250 ml, buchner funnel, measuring cup, volumetric pipette, upright cooler, electric
stove, and burette
Method
1. Modified Cassava Starch

Cassava

Weighed, peeled, and

weighed the netto

Sliced about 2cm

Yeast or lactic
acid bacteria
Soaked by yeast or lactic acid
bacteria solution for 24 hours

Dried on the sunlight

Milled ad sifted

Modified
cassava starch

2. Partial parboiling cassava(Rava) 3. Farina

Cassava Cassava

Weighed, peeled, and Weighed, peeled the

weighed the netto skin

Sliced about 2cm Grated and Squeezed

Boiled for 5 minutes and Pulp is roasted to dryness

drained

Milled ad sifted
Dried on the sunlight

Milled ad sifted Farina

Rava
4. Gari 5. Gaplek

Cassava Cassava

Weighed, peeled the Weighed, peeled the

skin skin

Slice about 2cm Grated

Soaked b yeast or lactic Soaked by NaCl colution

acid bacteria solution for 5% for 30 minutes
24 hours
Dried on the sunlight or oven Dried on the sunlight or oven

Milled ad sifted Milled ad sifted

Gari Gaplek

1. Cross-linking starch

Starch

Dissolved citric acid by distilled water and control pH

On tera

Starch is put to the solvent and moved to the dryer tray

Let stand for 16 hours in room temperature

Oven 60oC for 6 hours then 130oC for 2 hours

Washed by aquades and filtered by using filter glass 3G3

Rinsed by ethanol 96%, then by methanol and air dried

Mashed starch

Starch citrate
2. Cold water soluble starch

Starch

Suspended in ethanol and stirred

Added NaOH while stirring

Stirred and added ethanol

Keep in the room temperature

Starch is washed by ethanol and neutralized by HCl

Precipitate is washed with ethanol and dried in the oven

oven

3. Pirodextrin Modified starch 4. Heat Moisture treated starch

Starch Starch

Sprayed with HCl Suspended 50%

Stirred evenly Poured to bake sheet and dried to oven

Roasted for 30-60 minutes Milled and sifted

Modified starch Modified starch

4. Oxidized starch 5. Lintnerized starch

Starch Starch

Controlled pH until 9 with NaOH Mixed with HCl

Put to 30oC Stored for 7 days in the

room temperature
Added hipoclorite drop by drop
and stirred Washed and neutralized
with water and NaHCO3
Mixture is filtered and suspended solution
by aquades
Dried in the oven
pH is controlled until 6.5-7.0

Modified starch
Sample is washed with
water
Dried in the oven 50oC

Modified Starch

1. Iod Test 2. Granule form

Starch Starch

Put to the test plate Put the small amount on

the object glass
Dropped iod solution
Object glass is covered by
cover glass
Observed the changing color

Observed to the
Identified amylose microscope
and amylopectin
Draw starch granule
3.Apparent viscosity 4. Clarity of pasta

Modified Starch Starch pasta

Heated until boil for 15 minutes Put into screw tube

Cooled down to 25oC Dipped into boiling

water for 30 minutes
Pasta is measured by
viscosimeter broofield Shaken every 5 minutes

Cooling down in the room

Tested on rate 2,4,10, and 20
temperature
rpm
Observed on the
1,2,3,4,5,10,15,20, and 30 Read the transmittance value
minute of the spectrophotometer with
650nm wave

Starch
viscous Clarity of
pasta

RESULT AND DISCUSSION

Result

[attached]

Discussion

Starch is one of the most widely available materials in nature. Most

starches are stored in tuber(cassava, sweet potatoes, potatoes,etc.), seeds(corn,
rice, wheat), stems(sago) and fruit. Starch can be divided into 2 types, namely
natural starch which has not been modified (Native Starch) and modified starch.
Natural starch is obtained from the separation of starch found in both plants from
tubers, seed and stems. In its natural form starch is a small granule often called a
granule. Starch modification can be broadly grouped into four classes namely:
physical, chemical, enzymic and biological modifications. Among these
modification methods, chemical means is the most frequently used process
(Daramola and Osanyinlusi, 2006). Chemical modification of starch involves the
treatment of native starch with specific chemicals reagent. This definition includes
acetylated, oxidized, lintnerized, pyrodextrinized, hydroxypropylated and cross-
linked starches (Kaur et. al., 2004).
There are six kinds of modified cassava flour they are modified cassava
flour by using dry yeast and using lactic acid bacteria, partial parboiling cassava
flour(Rava), farina, gari, and gaplek (Table 1). Dry yeast and Lactic Acid
Bacteria (BAL) are a method to modified cassava flour with soaking the slicing
tuber into these starter. During soaking will occur fermentation that can change
the morphologi of starch granule. The yield of dry yeast production is 28,9%
while from BAL, the yield produce is 26.01%.
Partial parboiling cassava flour or called as rava is a traditional technique,
largely applied in the case of “ubi kayu” to improve its nutritional and textural
properties. During parboiling, the morphology of starch granule changes due to
their swelling and fusion (Bor and Mickus 1979). Making rava is almost the same
as making modified cassava flour. The difference is that immersion is not done in
rava processing but boiling is carried out for 5 minutes. That makes the tubers'
water levels more. Therefore, drying the tubers is done longer, ie for 36 hours.
Furthermore, the dried tubers are milled and sieved with 80 mesh sieves to
produce rava. The yield of production rava is 34.36%.
Farina is a modified product from tuber that through pressing process first
to get its extract and done roasting process to reduce the water content and drying
evenly. The value of yield of farina production is obtained 17,01%. While Gari
flour is the product of cassava which is processed into powder form through a
process of fermentation. This fermentation occur in 2 stages, in the first stage,
certain microorganism hydrolyse starch into glucose, next to lactic acid bacterias
will convert glucose into lactic acid and producing various other organic acid so
reduce the pH. Acid condition will support the growth of certain bacteria which
produce aldehyde and ester that give distinctive aroma (Prabowo 2011). So it
means, this flour is very suitable to make a bread that has distinctive aroma. The
yield of gari flour production from this laboratory can’t be identified because
there are several error that make gari flour can’t be produced.
Gaplek is very popular in Java which lacks water as a staple food. Based
on its shape, gaplek is divided into 5 groups, namely:1) log gaplek, 2) gaplek
chips 3) pellets, 4) gaplek flour and 5) gaplek cube. In general, logs and pellets are
used as raw material for animal feed, while gaplek flour is used as food
ingredients. Gaplek chips is used as an industrial material for starch, dextrin, and
glucose (Oramahi, 2005). Based on the data obtained, the yield of the gaplek
production 66,58%. This yield it the biggest value that obtained than all product.
 The iodine test is carried out by adding an iodine solution to the
polysaccharide which will form a specific colored adsorption complex. Amylum
or starch produces blue, dextrin produces grape red, while glycogen and some
hydrolyzed starches will form red (Star 2010). Based on the experiments of
modified starch, starch citrate, pyrodextrin, heat-moisture treated starch, oxidized
starch, and linteritzed starch produce purple, while Cold water soluble starch
produces a brownish purple color. In modified starch for cold water starch starch
produces white purple, pyrodextrin material produces purple, citrate starch
produces blackish purple, and heat moisture and oxidized material produces a
blackish blue color. The more concentrated blue-black color that arises indicates
the longer the chain of polysaccharides or the more starch contained. Starch in an
acidic atmosphere when heated can be hydrolyzed into simple compounds.
Crosslinking is done by making a chemical bond that connects the
hydroxyl (-OH) group of two starch molecules in the granule. Chemicals used
include a mixture of adipic acid and acid anhydride, phosphorus oxychloride,
sodium, trimethaphosphate, epichlorohydrin, and others. Cross ties are carried out
wet in alkaline conditions. The process is influenced by pH, temperature, process
duration. Cross-linking causes changes in the nature of starch, namely stronger
granules (not easily swelling / high swelling, high viscosity, acid resistance (low
pH), resistant to stirring (shearing), resistant to cooking at high temperatures.
Acid hydrolysis (acid thinning) is a hydrolysis of glycoside bonds
randomly producing fragments with a lower degree of polymerization, decreasing
heat viscosity, increasing gel strength, increasing the clarity of gel or paste. Acid
hydrolysis can be done in a dry or wet manner. Acid used by HCl, H2SO4. The
hydrolysis process is faster at high acid concentrations and or high temperatures.
The dry process produces dextrin which is more soluble with lower viscosity,
more hygroscopic, more sticky and forms films (as a coating). Starch which has
undergone acid treatment is widely used in candy products, especially sugered
candy.
 Wurzburg (1989) stated that acid-modified starch was made by
hydrolyzing starch with acid below the gelatinization temperature, at a
temperature of around 125oF (52oC). The basic reaction includes cutting the α-
1,4-glycosidic bonds from amylose and -1,6-glycosidic from amylopectin, so that
the size of the starch molecule becomes lower and increases the tendency of the
paste to form a gel. Acid-modified starch has a lower heat paste viscosity, greater
retrogradation tendency, cold starch paste viscosity ratio than lower hot starch
paste, granules which expand during gelatinization in lower hot water, increased
stability in warm water below gelatinization temperature and alkali number
higher.
Modification of starch with acid can reduce hot paste viscosity, reduce
hardness and gel strength. Giving acid will cause a decrease in hot paste viscosity
which is faster than the decrease in gel strength. The comparison of hot paste
viscosity with the hardness and breakdown strength of the gel from acid-modified
starch with unmodified starch will increase with increasing acidity. If the strength
of gelation is defined as the ratio between hot paste viscosity and cold paste
viscosity under standard conditions of acid modified starch which has the same
fluidity, then the strength of gel formation increases with increasing acid
concentration and decreasing treatment time, conversely if acid concentration
decreases and reaction time increases hence the strength of gel formation will
increase
Oxidation is done using hydrogen peroxide, peracetic acid, ammonium
persulfate, sodium hypochlorite. This process is done wet. In this process pigment
oxidation occurs, hydroxyl oxidation becomes carboxyl and carbonyl. This
process causes changes in the nature of starch, which is whiter color, not easily
retrogradation, and softer gel. Schoch et al (1959) suggested that the mechanism
of gel formation and retrogradation was caused by forming hydrogen bonds
between the hydroxy groups of the amylose chain and other amylose molecules.
The oxidation of this OH group prevents hydrogen bonds from filling the polymer
chain and the gel produced by its soft and short texture from natural starch.
Native starches have an ordered granule structure based on crystalline
lamellar platelets that are oriented with their large plane parallel to the surface of
the granule (French 1984). Irradiation of native starches with x-rays yields the A
or B diffraction patterns. The crystal structure is thought to consist of double
helices on amylopectin molecules packed within the lamellar platelets (Kainuma
and French 1972). The enthalpy required to separate the helical strands is the
“heat of gelatinization” which is conveniently measured by differential scanning
calorimetry IS. GCWS starch does not require heating for gelatinization,
suggesting that the structure of the granule has changed.
HMT method can change the characteristics of starch by increase the
gelatinization temperature, increase the viscosity of starch paste, and increase the
tendency of retrogradation (Adebowale et al 2005). The cyrstalin starch structure
impove along with higher temperature (above gelatinization temperature), so that
starch has perfectly gelatinized. In other hand a previous research done by Pranoto
et al. (2014) which is used the period of HMT time stated that with the longer
HMT will increased solubility due to the weakness of molecular binding of starch
intermolecul. According to Syamsir, et al. (2012) the changes of the starch
molecular that is lead to increase TDF will be not proceed under moisture content
(<20%) and lower temperature.
Lintnerized is one of ways for RS3 formation. Lintnerized starch is
obtained by mild acid hydrolysis of α-1,4 and α-1,6 glycosides linkages from
amylose and amylopectin. This method increases crystalline content, which
becomes resistant by enzymatic hydrolysis. Reference [4] has investigated that
resistant banana starch is obtained 16% from this method, and then autoclaved, its
shows a lower solubility in water than native starch and RS value is higher than
only lintnerized treatment. Besides that, Aparicio’s research (Saguilan et al 2005)
has showed that resistant starch prepared by lintnerizedautoclaved contained
slowly digestible carbohydrate. Zhao and Yang (Zhao and Lin 2009) suggested
that utilization citric acid to de-branch on RS type III formation is better than
hydrochloric acid and acetic acid.
The apparent viscosity measurement in this study was carried out using
Brookfield Viscometer with a material concentration of 5%. The viscosity value
will decrease with an increase in shear rate. The shear rate is a mechanical
collision in the paste starch solution which comes from the spindle rotation of the
Brookfield Viscometer tool. The higher the shear rate, the faster the spindle
rotation of the Brookfield Viscometer and the mechanical collisions that occur
will also increase. Increasing mechanical collisions will increase the flowing
properties of the starch paste solution and will further reduce the friction force.
This is what causes a decrease in the value of viscosity. The decrease in viscosity
due to an increase in shear rate indicates that the rheological conditions of starch
solutions are pseudoplastic. The apparent viscosity is not only caused by the
development of starch granules, but also by the presence of dissolved starches
which resist the development of granules by adhesion, and also by interactions
between the expanding granules (Astuti 2009). Prepared acid-modified starches
with varying levels of gel formation at the same fluidity, because the strength of
gel formation increased due to increased acidity and decreased reaction time
and conversely a decrease in acid concentration would increase reaction time.
The viscosity of acid-modified starch will decrease if the acid content is
increased.
Clarity of pasta is one of the important parameters in determining the
quality of starch paste in addition to the viscosity of the paste, mainly based on
visual appearance related to the clear or opaque nature of the paste produced. But
there are also foods that require starch paste to form opaque as in salad dressings
(Winarno 2002). Paste clarity from groups 1 to 6 respectively, namely 7,0%,
89,5%, 85,8%, 74,2%,98,6%, and 34,0% while the clarity of the paste from the
blanko is 100(Table 5). The highest value for clarity of pasta is group 5 with
oxidized starch while the small one is group 1 with citrate starch. There are error
in this test because according to Starch granules consist of two fractions, namely
crystalline and amorphous fraction. The crystalline fraction is difficult to dissolve
in water, while the amorphous fraction dissolves easily in water. During the
fermentation process, the amorphous fraction in the acid tapioca granule is cut off
so that it is increasingly many parts that are soluble in water. Thus, the clarity of
the paste will be higher (Sari 20112)
 CONCLUSION AND SUGGESTION

Conclusion

There are six kinds of modified cassava flour they are modified cassava
flour by using dry yeast and using lactic acid bacteria, partial parboiling cassava
flour(Rava), farina, gari, and gaplek. The highest yield is obtained by gaplek flour
while the smallest one is obtained by farina flour. For the clarity of pasta, group 5
with oxidized starch get the highest value for clarity of pasta while the small one
is group 1 with citrate starch. To analyze the characteristics of flour and modified
starch that has been produced, iodine testing, calculation of mass balance,
apparent viscosity, and clarity of paste. The flour this modified method of flour
and starch production was analyzed by iodine test. This test detects the content of
starch contained in the material used. This clarity test was carried out using
modified starch ingredients, namely starch citrate, cold water soluble strach,
pyrodextrin, heat moisture treat and strach, oxidied strach, and lintnerized strach.

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Aparicio-Saguilán A, Flores-Huicochea E, Tovar J, García-Suárez F, Gutiérrez-
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ATTACHMENT

Tabel 1 Neraca Massa Tepung Kasava Termodifikasi

Kelompok Perlakuan Bobot total (g) Bobot tepung (g) Rendemen (%)
1 Dry yeast 614 177,46 28,9
2 BAL 984 255,92 26,01
3 Rava 450,4 154,325 34,26
4 Farina 854,6 145,355 17,01
5 Gari 930,1 - -
6 Gaplek 393,2 261,79 66,58

Tabel 2 Hasil pengamatan uji iod tepung

Kelompok Mocaf Pati Termodifikasi Tepung Singkong Pati Singkong

1 Ungu kehitaman Ungu Ungu kehitaman Ungu kehitaman
2 Ungu Ungu kecoklatan Ungu kecoklatan Ungu kehitaman
3 Ungu kehitaman Ungu Ungu kehitaman Ungu kehitaman
4 Ungu Ungu Ungu Ungu kehitaman
5 Ungu Ungu Ungu Ungu
 6 Ungu Ungu Ungu Ungu

Tabel 3 Hasil pengamatan bentuk granula pati

Kelompok Bahan Gambar Keterangan

1 Pati Sitrat Bulat

Cold water soluble

2 Kecil tidak beraturan
Starch

3 Pirodekstrin Bulat

Heat-moisture treated
4 Oval
Starch

5 Oxidized starch Bulat teratur

6 Lintnerized starch Bulat teratur

Tabel 4 Hasil pengamatan Apparent Viscosity

Menit Rata-
Kel. Bahan
0 1 2 3 4 5 10 15 20 rata
1 Dry yeast 664 688 688 616 692 660 648 652 644 661,33
2 BAL 160 180 159 160 150 122 145,8 138,4 135,4 150,07
3 Rava 40 80 112 104 112 100 93,2 91,2 120 94,71
4 Farina 150 150 150 150 125 145 150 150 130 144,44
5 Gari 4300 4250 4200 4325 4200 4275 4615 4675 4560 4404
6 Gaplek 526,4 520 533,2 520 520 520 520 520 520 522,18

Tabel 5 Hasil pengamatan kejernihan pasta

 Nilai Trasmittance Pati
Kelompok
Termodifikasi (%T)
1 7,0
2 89,5
3 85,8
4 74,2
5 98,6
6 34,0
Blanko : 100