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HYDROLYSATION- A REVIEW.
Abstract
Cassava (Manihot esculenta crantz) is a perennial tuber plant widely grown in many
tropical countries including Nigeria as one of the most important commercial crops.
Cassava is an important high energy traditional food crop yielding 250 x 103 Cal. ha-1
2
product.
quality of extracted starch. The long
residence time can also promote
2.2 Rasping of Cassava Roots
microbial growth bringing about
breakdown of starch and resultant loss
Washed roots are transported via
of starch quality. Besides, the presence
conveyor belt to a root chopper. Inside
of these microorganisms affects the
this machine, the cassava roots are
colour of the starch limiting its use in
chopped into smaller pieces with large
food and textile applications.
cutting blades. The chopped roots are
then taken to a rasper. During rasping,
Table 1: Biochemical contents of
water is used to facilitate the process. The
cassava starches.
resulting suspension (rasped fresh pulp)
consists of starch, water, fibre, and other
Moisture [%] 14.8a, 10-13b
impurities. In general, a small rasper
drum, with a high number of blades per
Fibre/ash [%] 0.02-0.49c, 0.33d,
surface area, is used with rather low
0.22 , 0.32 , 0.1-0.8 , 0.01-0.029f
e a b
speed to avoid such a fine pulp that may
create difficulty in starch extraction
Lipid [%] 0.1-1.54g, c, d, h,
which could lead to low production
0.96e, 0.1-0.4b, 0.07-0.73f
efficiency
Phosphorus [%] 0.007-0.012c ,
2.3 Starch Extraction 0.0075e
3
Aqueous ammonia (0.03 M), when The medium phase liquid contains
used for starch extraction, not only small starch granules and fine pulp. It
improved the yield, but also the can be reused in the process but fine
functional characteristics such as paste pulp has to be removed first. The light-
viscosity and swelling. Ammonia acts phase liquid has less impurities and
by complexing with the mucilagenous can be reused. The 3-phase machine
material releasing the starch granules uses a less water and reduces the
and enabling faster settling of starch in number of steps in separating the
less viscous slurry. Kallabinski and starch. In the use of a hydrocyclone to
Balagopalan (1994) developed an facilitate the separation of impurities
enzymatic method for enhancing the and chemicals from starch slurry and
recovery (26 % increase) of starch the installation of a densitometer to
from cassava tubers using pectinase measure the concentration of starch
and cellulase enzymes. These enzymes slurry are also necessary to obtain
alter the integrity of the pectin- starch slurry and starch product with
cellulosic matrix of cell membranes consistent quality. The starch slurry
and thereby facilitate the release of the from the separators is pumped to a
starch granules. Mathew et al., (1995) dewatering centrifuge. With filter cloth
used a mixed culture inoculum to placed inside it, rotates at about 1,000
enhance the yield of starch from rpm to remove water from the starch
cassava tubers. Although the recovery slurry.
of starch increased, the starch was
invariably contaminated with fibrous 2.4 Drying Process
material.
Cassava starch is dried using a
The starch slurry from fine extractors pneumatic conveying dryer. A burner
is purified and concentrated in a is generally used to generate heat.
separator. Generally, a 2-phase nozzle There are two types of burners in use
type separation machine is used. This today: hot air burners and thermo-oil
method utilizes centrifugal force boilers. Air, heated to 170 to 200 0C, is
created by rotating the machine at used to dry the starch cake in a flash
about 3,000 rpm. The liquid that dryer. The starch is transferred to a
enters the machine is separated into drying cyclone and then a cooling
two phases: concentrated starch slurry cyclone. The dried starch is then sifted
and clear water with impurities to assure uniform particles and
(mostly used to wash the roots). The packaged.
final starch slurry obtained is held at
The most important characteristics of
18-20 oBe as it enters the dewatering
cassava starch are odorless, paste clarity
process.
and stickiness. These remarkable
To improve the separation process, a
characteristics of cassava starch are
3-phase nozzle type separation
enabling to be conveniently and readily
machine has been developed. This uses
with other flavoring and coloring agents.
the same principles as the 2-phase
machine, but the liquid is separated 3.0 Starch granule size and
into three phases: the heavy phase, the microscopic appearance
medium phase, and the light phase. Starch granules in storage tissues can vary
in shape, size and composition. The shape
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and size of the granules depends on the medium (10–25 µm), small (5–10 µm)
source, which allows one to identify the and very small (<5 µm) granules. Cassava
botanical source of the starch by starch granule is large within the range of
microscopic examination (Preiss, 2004). 4-35 µm.
In general, granule size may vary from Cassava starch granules are mostly round
less than 1 µm to more than 100 µm. with a flat surface on one side containing
Generally, granule size is expressed as the a conical pit, which extends to a well-
average spherical equivalent diameter. defined eccentric hilum (Moorthy, 1999).
No precise categorization of granule size The native surface of most granules
was found in the literature (Lindebooma appears smooth without observable
et al., 2004). For this reason, the following pores as shown below.
classes are defined: large ( 25 µm),
Fig. 1: Cassava starch granule with magnification 1500x (Whistler et al., 1984)
The granule size is reported to affect some cassava starch granule are responsible for
functional properties of cassava such as less susceptibility of cassava starch to α-
swelling, solubility and digestibility. The amylase hydrolyzation.
study of acid and enzymatic hydrolysis of It has been reported that enzymatic
granular starches can provide information hydrolysis of granular cassava starch at
about the structure of these granules temperatures below the starch
(Franco et al. 1988). The effect of starch gelatinization temperature results in a
granule size on enzymatic susceptibility pitted and porous granule surface, which
has been studied by various authors is readily discernible by microscopic
(Franco and Ciacco, 1992), and many of examination (MacGregor and Balance,
them have observed that the large size of 1980). Franco and Ciacco (1992), also
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reported that enzymatic attack on the arrays of the double helices then form
cassava granules are characterized by crystallites. The alternating zones of
considerable surface corrosion, mainly at different densities of amylopectin account
the radial axis. for the crystalline and amorphous phases
of starch. Amylose occurs predominantly
in the amorphous phase (Seib, 1997). It is
4.1 Structure and organisation of now widely accepted that the amylopectin
starch is predominantly responsible for granule
Starch is unique among carbohydrates crystallinity.
since it naturally occurs as tiny granules. A starch granule observed under
The starch granule organization is very polarized light shows a maltese cross,
complicated and depends strongly on the indicating through this birefringence
botanical origin. The amylose and phenomenon, a semi crystalline structure.
amylopectin fractions are considered to be Looking at acid hydrolysis treated starch
oriented in the starch granule in radical (acid will cut the glucose bonds allowing
fashion (Wurzburg, 1986). Hydrogen water to penetrate the granule more
bonds between adjacent linear segments easily) under light microscope it is
of the amylopectin or amylose molecules possible to see concentric growth rings
segments may form micellar crystallites (mainly for large granule). The initial
which are responsible for the granule growth centre is called the hilum. These
integrity and for imparting birefringent growth rings are a succession of
properties which are manifested by alternated amorphous and crystalline
polarization crosses. These polarization zones (Fig. 2) thus, suggesting that starch
crosses are characteristic for intact starch matures in a diurnal rhythm, and that
granules (Wurzburg, 1986). In a cluster of newly synthesized material is deposited
amylopectin, two neighbouring chains on the surface as the granule increases in
intertwine into a double helix. The linear size (Oates, 1997).
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Fig. 2: Schematic view of the structure of a starch granule, with alternating amorphous
and semi-crystalline zones constituting the growth rings (Jenkins and Donald, 1995).
8
Single stage gelatinisation When cassava starch was subjected to
with high peak viscosity and steam-pressure treatment, the viscosity
high viscosity breakdown fell steadily with increase in pressure and
Two-stage gelatinisation time of treatment. In addition to peak
with high peak viscosity and viscosity, the breakdown in viscosity is
breakdown another important criterion that decides
Broad two-stage the applicability of starch in food and
gelatinisation with medium industry. In this respect, cassava starch is
viscosity and medium considered inferior to maize starch,
breakdown. because its viscosity is rapidly lowered on
These patterns seem to be genetically heating under shear leading to a ‘long’ and
controlled as the patterns were cohesive texture for its paste, which is not
maintained by these starches irrespective desirable in food and textile applications.
of the environmental factors, though there
was variation in the viscosity values.
between the starch molecules in the
4.5 Solubility granules. Because of its weaker
associative forces cassava starch has a
Solubility of starch depends on a number better clarity than cereal starches. The
of factors such as source, inter-associative reduction in clarity on pressure treatment
forces, swelling power, presence of other can be attributed to the strengthening of
components, e.t.c. Moorthy and associative forces (Moorthy, 1999).
Ramanujam (1986) reported that
wherever the granules have low swelling 5. Cassava starch hydrolysis
volume they have high solubility showing
that during the growth period due to One of the most important enzymatic
environment and associated physiological reactions that is carried out at an
changes the strength of binding industrial scale is the enzymatic
(associative) forces between the hydrolysis of starch. α-Amylase (1,4-α-d-
molecules in starch granules are reduced glucanohydrolase, EC 3.2.1.1) is essential
considerably in certain varieties leading to during this process and plays a role in the
a very low swelling volume and high liquefaction of starch and the subsequent
solubility. Cassava starch has a higher saccharification where larger
solubility than the other tuber crop carbohydrate chains are hydrolysed and
starches and the higher solubility can be converted into smaller carbohydrates
attributed partly to the high swelling (Chaplin and Bucke, 1990).
cassava starch undergoes during The studies have shown that starches vary
gelatinisation. The solubility values in their resistance to the action of α-
ranged from 25 to 48 % (Rickard et al., amylase. Starches that naturally show a
1991). The solubility of starch of different porous surface, such as corn starch, are
cassava varieties varied from 17.2 to 27.2 more easily degraded than those with
%. smooth surfaces, such as cassava starch
(Franco et al. 1988). Cassava starch
4.7 Clarity susceptibility to enzyme attack is
influenced by several factors, such as
The high clarity of starch has much amylose and amylopectin content (Dreher
relevance in food and textile applications et al., 1984; Hoover and Sosulski, 1985;
and depends on the associative bonds Ring et al., 1988), crystalline structure,
9
particle size and the presence of enzyme of cassava and corn starches. Corn starch
inhibitors. Among these factors, granular revealed a more susceptible structural
structure is believed to be the most nature under attack by α-amylase or α-
important (Zhang and Oates, 1999). Corn amylase plus amyloglucosidase than
starch is more susceptible to hydrolysis cassava starch. By the use of light
than cassava starch when the reaction microscope, it could be seen that the
products are not eliminated, these results enzymatically treated corn starch was
indicated that the hydrolysis products frequently broken, while the cassava
obtained from cassava starch were more starch, even under the heaviest amylolytic
efficient in inhibiting enzyme action conditions, was comparatively less altered
(Franco et al., 1988). Among non-cereal (Fig. 3) (Franco et al., 1988). In fact,
starches, cassava starch has a relatively cassava starch under α-amylase treatment
higher enzyme susceptibility than other was mildly exo-corroded (Fig. 3b). The
starches (Rickard et al., 1991), whereas same treatment applied to corn starch
potato starch shows stronger resistance to attacked the surface deeply and also the
enzyme attack. Sweet potato starch is inner granule parts (Fig. 3e).
more susceptible than potato starch but Characteristic lamellae arrangement was
less susceptible than cassava starch to α- displayed after α-amylase treatment (Fig.
amylase and glycoamylase attack 3f and 3g). In fact, these figures suggest
(Delpeuch and Favier, 1980; Hizukuri et that the lamellae are not just planes of
al., 1988; Kainuma, 1988). homogeneous and regular highly
In the hydrolysis of starch, enzyme does crystalline compact organization, but
not penetrate freely through the granule planes that conceal a linear core,
molecular unit, but is limited to certain susceptible to degradation under those
areas (Franco and Ciacco, 1987). Scanning enzymatic conditions. Furthermore,
electron microscope (SEM) observations transverse connections were observed
revealed differences in the enzyme attack that bonded the lamellae.
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Figure 3: Scanning electron micrographs of cassava and corn starches “in natura” or
enzymatically treated (Franco et al., 1988).
(a) cassava starch “in natural” (1500x),
(b) cassava starch with α-amylase treatment: mild exocorrosion occurs (2000x),
(c) cassava starch, same conditions plus amyloglucosidase: same radial channels of corrosion
appear (2000x),
(d) corn starch “in natural”,
(e) corn starch with α-amylase treatment:numerous radial channels of corrosion show it to be
more suspectible than cassava starch (4500x),
(f) corn starch treated with α-amylase: the radial channels of corrosion split the granule.
exhibiting the lamellae arrangement.This enzymatic attack revealed an inner disruption inside
the lamellae as well as bridges of resisting structures bonding the lamellae perpendicularly
(10000x).
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properties of starch. Starch/Stärke. of Dioscorea ballophylla and
50: 72-77. Amorphaphalus campanulatus.
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