STARCH AND GLYCOGEN

NAME : T.L.V.PEIRIS
DEPARTMENT:FOOD SCIENCE
UNIVERSITY: UNIVERSITY OF SRI JAYAWARDENAPURA
YEAR : AUGUST 2009
STUDENT NUMBER: GS/MSc/Food/3630/08
Summery

This report gives you what is starch and what is glycogen. It includes the molecular
structures of starch and glycogen and what are the components that it is made of, their
industrial applications and how the synthesis and breakdown of glycogen occur. Further
this report contains identification tests for starch and about starch granules. It further
explains the hormonal activities of glycogen synthesis and characteristics which made
these two molecules good storage molecules.

Key words: amylopectin, amylase, crystallinity, glycogen metabolism

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Contents page number

Introduction 04

Structural units 04-09

Molecular structure

Amylose

Amylopectin

Functionality 09-10

Industrial applications 10- 12

Identification tests 12-13

Starch is a good for storage carbohydrate 13

Glycogen 13-14

Function and regulation of liver glycogen 14-15

In liver

In muscle and other cells

Synthesis

Breakdown

Glycogen debt and endurance exercise 18

Disorders of glycogen metabolism 18

Why Glycogen as an Energy Storage Molecule 19

Reference

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Introduction

Starch or amylum is a polysaccharide carbohydrate consisting of a large number of

glucose units joined together by glycosidic bonds. Starch is the major carbohydrate
reserve in plant tubers and seed endosperm where it is found as granules, each typically
containing several million amylopectin molecules accompanied by a much larger number
of smaller amylose molecules. By far the largest source of starch is corn (maize) with
other commonly used sources being wheat, potato, tapioca and rice. Amylopectin
(without amylose) can be isolated from 'waxy' maize starch whereas amylose (without
amylopectin) is best isolated after specifically hydrolyzing the amylopectin with
pullulanase . Genetic modification of starch crops has recently led to the development of
starches with improved and targeted functionality.

Structural units

Starch consists of two types of molecules, amylose (normally 20-30%) and amylopectin
(normally 70-80%). Both consist of polymers of α-D-glucose units in the 4C1
conformation. In amylose these are linked - (1 4)-, with the ring oxygen atoms all on
the same side, whereas in amylopectin about one residue in every twenty or so is also
linked - (1 6)- forming branch-points. The relative proportions of amylose to
amylopectin and - (1 6) - branch-points both depend on the source of the starch, for
example, amylomaizes contain over 50% amylose whereas 'waxy' maize has almost none
(~3%)

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 Representative partial structure of amylase

Representative partial structure of amylopectin

Molecular structure

Amylose and amylopectin are inherently incompatible molecules; amylose having lower
molecular weight with a relatively extended shape whereas amylopectin has huge but
compact molecules. The presence of amylose tends to reduce the crystallinity of the
amylopectin and influence the ease of water penetration into the granules. Most of their
structure consists of α-(1 4)-D-glucose units. Although the α-(1 4) links are capable
of relatively free rotation around the (φ) phi and (ψ) psi torsions, hydrogen bonding
between the O3' and O2 oxygen atoms of sequential residues tends to encourage a helical
conformation. These helical structures are relatively stiff and may present contiguous
hydrophobic surfaces.

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Amylose

Amylose molecules consist of single mostly-unbranched chains with 500-20,000 α-(1

4)-D-glucose units dependent on source (a very few α-1 6 branches and linked
phosphate groups may be found .But these have little influence on the molecule's
behavior. Amylose can form an extended shape (hydrodynamic radius 7-22 nm) but
generally tends to wind up into a rather stiff left-handed single helix or form even stiffer
parallel left-handed double helical junction zones . Single helical amylose has hydrogen-
bonding O2 and O6 atoms on outside surface of the helix with only the ring oxygen
pointing inwards. Hydrogen bonding between aligned chains causes retrogradation and
releases some of the bound water (syneresis). The aligned chains may then form double
stranded crystallites that are resistant to amylases. These possess extensive inter- and
intra-strand hydrogen bonding, resulting in a fairly hydrophobic structure of low
solubility. The amylose content of starches is thus the major cause of resistant starch
formation .

Single helix amylose behaves similarly to the cyclodextrins by possessing a relatively

hydrophobic inner surface that holds a spiral of water molecules, which are relatively
easily lost to be replaced by hydrophobic lipid or aroma molecules. It is also responsible
for the characteristic binding of amylose to chains of charged iodine molecules (for
example, the polyiodides; chains of I3- and I5- forming structures such as I93- and I153-; note
that neutral I2 molecules may give polyiodides in aqueous solution and there is no
interaction with I2 molecules except under strictly anhydrous conditions) where each turn
of the helix holds about two iodine atoms and a blue color is produced due to donor-
acceptor interaction between water and the electron deficient polyiodides.

Amylopectin

Amylopectin is formed by non-random α-1 6 branching of the amylose-type α-(1

4)-D-glucose structure. This branching is determined by branching enzymes that leave
each chain with up to 30 glucose residues. Each amylopectin molecule contains a million
or so residues, about 5% of which form the branch points. There are usually slightly more
'outer' unbranched chains (called A-chains) than 'inner' branched chains (called B-
chains). There is only one chain (called the C-chain) containing the single reducing group

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A-chains generally consist of between 13-23 residues. There are two main fractions of
long and short internal B-chains with the longer chains (greater than about 23-35
residues) connecting between clusters and the shorter chains similar in length to the
terminal A-chains

Each amylopectin molecule contains up to two million glucose residues in a compact

structure with hydrodynamic radius 21-75 nm. The molecules are oriented radially in the
starch granule and as the radius increases so does the number of branches required to fill
up the space, with the consequent formation of concentric regions of alternating
amorphous and crystalline structure. In the diagram below: A - shows the essential
features of amylopectin. B - shows the organization of the amorphous and crystalline
regions (or domains) of the structure generating the concentric layers that contribute to
the “growth rings“ that are visible by light microscopy. C - shows the orientation of the
amylopectin molecules in a cross section of an idealized entire granule. D - shows the
likely double helix structure taken up by neighboring chains and giving rise to the
extensive degree of crystallinity in granule. There is some debate over the form of the
crystalline structure but it appears most likely that it consists of parallel left-handed
helices with six residues per turn. An alternative arrangement of interconnecting clusters
has been described for some amylopectins.

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Some amylopectin (for example, from potato) has phosphate groups attached to some
hydroxyl groups, which increase its hydrophilicity and swelling power. Amylopectin
double-helical chains can either form the more open hydrated Type B hexagonal
crystallites or the denser Type A crystallites, with staggered monoclinic packing,
dependent on the plant source of the granules. Type A, with unbroken chain lengths of
about 23-29 glucose units is found in most cereals.

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Type B, with slightly longer unbroken chain lengths of about 30-44 glucose units is
found in banana, some tubers such as potato and high amylose cereal starches. There is
also a type C structure, which is a combination of types A and B and found in peas and
beans.

Functionality

Starch is a versatile and cheap, and has many uses as thickener, water binder, emulsion
stabilizer and gelling agent. Its form and functionality have recently been reviewed.
Starch is often used as an inherent natural ingredient but it is also added for its
functionality. It is naturally found tightly and radially packed into dehydrated granules
(about one water per glucose) with origin-specific shape and size (maize, 2-30 μm;
wheat, 1-45 µm; potato, 5-100 μm). The size distribution determines its swelling
functionality with granules being generally either larger and lenticular (lens-like, A-
starch) or smaller and spherical (B-starch) with less swelling power. Granules contain
'blocklets' of amylopectin containing both crystalline (~30%) and amorphous areas. As
they absorb water, they swell, lose crystallinity and leach amylose. The higher the
amylose content, the lower is the swelling power and the smaller is the gel strength for
the same starch concentration. To a certain extent, however, a smaller swelling power due
to high amylose content can be counteracted by a larger granule size. Although the
properties of starch are naturally inconsistent, being dependent on the vagaries of
agriculture, there are several suppliers of consistently uniform starches as functional
ingredients.

Of the two components of starch, amylose has the most useful functions as a
hydrocolloid. Its extended conformation causes the high viscosity of water-soluble starch
and varies relatively little with temperature. The extended loosely helical chains possess a
relatively hydrophobic inner surface that is not able to hold water well and more
hydrophobic molecules such as lipids and aroma compounds can easily replace this.
Amylose forms useful gels and films. Its association and crystallization (retrogradation)
on cooling and storage decreases storage stability causing shrinkage and the release of
water (syneresis). Increasing amylose concentration decreases gel stickiness but increases
gel firmness. Retrogradation is affected by lipid content, amylose/amylopectin ratio,
chain length of amylose and amylopectin, and solid concentration. Amylopectin
interferes with the interaction between amylose chains (and retrogradation) and its
solution can lead to an initial loss in viscosity and followed by a more slimy consistency.
Mixing with κ-carrageenan, alginate, xanthan gum and low molecular weight sugars can

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also reduce retrogradation. At high concentrations, starch gels are both pseudoplastic and
thixotropic with greater storage stability. Their water binding ability (high but relatively
weak) can provide body and texture to foodstuffs and is encouraging its use as a fat
replacement.

A significant proportion of starch in the normal diet escapes degradation in the stomach
and small intestine and is labeled 'resistant starch' (for a recent review see [991]), but this
portion is difficult to measure and depends on a number of factors including the form of
starch and the method of cooking prior to consumption. Nevertheless resistant starch
serves as a primary source of substrate for colonic microflora, and may have several
important physiological roles (see hydrocolloids and health). Resistant starch has been
categorized as physically inaccessible (RS1), (raw) ungelatinized starch (for example, in
banana; RS2 b ), thermally stable retrograded starch (for example, as found in bread,
especially stale bread, mainly amylose; RS3) and chemically modified starch (RS4).
Resistant starch should be considered a dietary fiber. Although not exactly quantifiable
due to its heterogeneous nature, some is determined by the official Association of Official
Agricultural Chemists (AOAC) method. Starch with structure intermediate between the
more crystalline resistant starch (for example, RS3 in staled bread) and more amorphous
rapidly digestible starch (for example, in boiled potato) is slowly digestible starch [293]
(for example, in boiled millet). Slowly digestible starch gives reduced postprandial blood
glucose peaks and is therefore useful in the diabetic diet

Many functional derivatives of starch are marketed including cross-linked, oxidized,

acetylated, hydroxypropylated and partially hydrolyzed material. For example, partially
hydrolyzed (that is, about two bonds hydrolyzed out of eleven) starch (dextrin) is used in
sauces to control viscosity.

Industrial applications

Papermaking is the largest non-food application for starches globally, consuming

millions of metric tons annually. In a typical sheet of copy paper for instance, the starch
content may be as high as 8%. Both chemically modified and unmodified starches are
used in papermaking. In the wet part of the papermaking process, generally called the
“wet-end”, the starches used are cationic and have a positive charge bound to the starch
polymer. These starch derivatives associate with the anionic or negatively charged paper
fibers / cellulose and inorganic fillers. Cationic starches together with other retention and
internal sizing agent help to give the necessary strength properties to the paper web to be
formed in the papermaking process (wet strength), and to provide strength to the final
paper sheet (dry strength).

In the dry end of the papermaking process the paper web is rewetted with a starch based
solution. The process is called surface sizing. Starches used have been chemically, or
enzymatically depolymerized at the paper mill or by the starch industry (oxidized starch).
The size - starch solutions are applied to the paper web by means of various mechanical
presses (size press). Together with surface sizing agent the surface starches impart
additional strength to the paper web and additionally provide water hold out or “size” for

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superior printing properties. Starch is also used in paper coating as one of the binders for
the coating formulation a mixture of pigments, binders and thickeners. Coated paper has
improved smoothness, hardness, whiteness and gloss and thus improves printing
characteristics.

Corrugated board adhesives are the next largest application of non-food starches
globally. Starch glues are mostly based on unmodified native starches plus some additive
such as borax and caustic soda. Part of the starch is gelatinized to carrier slurry of
uncooked starches and prevent sedimentation. This opaque glue is called a SteinHall
adhesives. The glue is applied on tips of the fluting. The fluted paper is pressed to paper
called liner. This is then dried under high heat, which causes the rest of the uncooked
starch in glue to swell/gelatinize. This gelatinizing makes the glue a fast and strong for
corrugated board production.

Another large non-food starch application is in the construction industry where starch is
used in the gypsum wall board manufacturing process. Chemically modified or
unmodified starches are added to the stucco containing primarily gypsum. Top and
bottom heavyweight sheets of paper are applied to the formulation and the process is
allowed to heat and cure to form the eventual rigid wall board. The starches act as a glue
for the cured gypsum rock with the paper covering and also provide rigidity to the board.

Adhesives - Starch is used in the manufacture of various glues for book-binding,

wallpaper adhesives, paper sack production, tube winding, gummed paper, envelop
adhesives, school glues, bottle labeling.

Starch derivatives as yellow dextrins can be modified by addition of some chemical

forms to be a hard glue for paper work, some of those forms are Borax, Soda Ash, which
mixed with the starch solution at 50-70 °C to gain a very good adhesive, Sodium Silicate
can be added to reinforce this formula.

Clothing starch or laundry starch is a liquid that is prepared by mixing a vegetable

starch in water (earlier preparations also had to be boiled), and is used in the laundering
of clothes. Starch was widely used in Europe in the 16th and 17th centuries to stiffen the
wide collars and ruffs of fine linen which surrounded the necks of the well-to-do. During
the 19th century and early 20th century, it was stylish to stiffen the collars and sleeves of
men's shirts and the ruffles of girls' petticoats by applying starch to them as the clean
clothes were being ironed. Aside from the smooth, crisp edges it gave to clothing, it
served practical purposes as well. Dirt and sweat from a person's neck and wrists would
stick to the starch rather than to the fibers of the clothing, and would easily wash away
along with the starch. After each laundering, the starch would be reapplied. Today the
product is sold in aerosol cans for home use.Starch is also used to make some packing
peanuts, and some dropped ceiling tiles.

Textile chemicals - To reduce breaking of yarns during weaving, the warp yarns are
sized. Starch is one of the main agents used for cotton sizing. Starch is also used as
printing thickener.

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Printing industry - in the printing industry food grade starch[9] is used in the
manufacture of anti-set-off spray powder used to separate printed sheets of paper to avoid
wet ink being set off.

Bioplastics - starch is used to produce various bioplastics, synthetic polymers that are
biodegradable. An example is polylactic acid.

Body powder - Powdered corn starch is used as a substitute for talcum powder in many
health and beauty products.

Oil exploration - starch is used to adjust the viscosity of drilling fluid which is used to
lubricate the drill head in (mineral) oil extraction.

Biofuel - Glucose from starch can be further fermented to ethanol.

Hydrogen production - Starch can be used to produce hydrogen, using enzymes.

Identification Tests
Iodine solution is used to test for starch; a darkblue color indicates the presence of starch.
The details of this reaction are not yet fully known, but it is thought that the iodine (I3−
and I5− ions) fits inside the coils of amylose, the charge transfers between the iodine and
the starch, and the energy level spacings in the resulting complex correspond to the
absorption spectrum in the visible light region. The strength of the resulting blue color
depends on the amount of amylose present. Waxy starches with little or no amylose
present will color red.

Starch indicator solution consisting of water, starch and iodine is often used in redox
titrations: in the presence of an oxidizing agent the solution turns blue, in the presence of
reducing agent the blue color disappears because triiodide (I3−) ions break up into three
iodide ions, disassembling the starch-iodine complex. A 0.3% w/w solution is the
standard concentration for a starch indicator. It is made by adding 4 grams of soluble
starch to 1 litre of heated water; the solution is cooled before use (starch-iodine complex
becomes unstable at temperatures above 35 °C).

Microscopy of starch granules - Each species of plant has a unique shape of starch
granules in granular size, shape and crystallisation pattern. Under the microscope, starch

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grains stained with iodine illuminated from behind with polarized light show a distinctive
Maltese cross effect (also known as extinction cross and birefringence).

Starch is a good storage of carbohydrates because:

1. It can fold up to take up less space inside the plant.

2. It is insoluable in water, meaning, it can stay inside the plant without dissolving.

3. It can be digested as "back up" energy in case there is less limiting factors like; Carbon
Dioxide, light, temperature or nutrients in the soil.

Glycogen

A core protein of glycogenin is surrounded by branches of glucose units. The entire

globular granule may contain approximately 30,000 glucose units.

Glycogen is the molecule which functions as the secondary short term energy storage in
animal cells. It is made primarily by the liver and the muscles, but can also be made by
glycogenesis within the brain and stomach. Glycogen is the analogue of starch, a less
branched glucose polymer in plants, and is commonly referred to as animal starch,
having a similar structure to amylopectin. Glycogen is found in the form of granules in
the cytosol in many cell types, and plays an important role in the glucose cycle. Glycogen
forms an energy reserve that can be quickly mobilized to meet a sudden need for glucose,
but one that is less compact than the energy reserves of triglycerides (fat). In the liver
hepatocytes, glycogen can compose up to 8% of the fresh weight (100–120 g in an adult)
soon after a meal. Only the glycogen stored in the liver can be made accessible to other
organs. In the muscles, glycogen is found in a much lower concentration (1% to 2% of
the muscle mass), but the total amount exceeds that in the liver. However the amount of
glycogen stored in the body, especially within the red blood cells ,liver & muscles,
mostly depends on physical training, basal metabolic rate and eating habits. Small
amounts of glycogen are found in the kidneys, and even smaller amounts in certain glial

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cells in the brain and white blood cells. The uterus also stores glycogen during pregnancy
to nourish the embryo.

Function and regulation glycogen

In liver

As a meal containing carbohydrates is eaten and digested, blood glucose levels rise, and
the pancreas secretes insulin. Glucose from the hepatic portal vein enters the liver cells
(hepatocytes). Insulin acts on the hepatocytes to stimulate the action of several enzymes,
including glycogen synthase. Glucose molecules are added to the chains of glycogen as
long as both insulin and glucose remain plentiful. In this postprandial or "fed" state, the
liver takes in more glucose from the blood than it releases.

After a meal has been digested and glucose levels begin to fall, insulin secretion is
reduced, and glycogen synthesis stops. About four hours after a meal Glycogen begins to
be broken down and converted again to glucose. Glycogen phosphorylase is the primary
enzyme of glycogen breakdown. For the next 8–12 hours, glucose derived from liver
glycogen will be the primary source of blood glucose to be used by the rest of the body
for fuel.

Glucagon is another hormone produced by the pancreas, which in many respects serves
as a counter-signal to insulin. When the blood sugar begins to fall below normal,
glucagon is secreted in increasing amounts. It stimulates glycogen breakdown into
glucose even when insulin levels are abnormally high.

In muscle and other cells

Muscle cell glycogen appears to function as an immediate reserve source of available

glucose for muscle cells. Other cells that contain small amounts use it locally as well.
Muscle cells lack glucose-6-phosphatase enzyme, so they lack the ability to pass glucose

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into the blood, so the glycogen they store internally is destined for internal use and is not
shared with other cells, unlike liver cells.

Synthesis

Glycogen synthesis differs from glycogen breakdown. Unlike breakdown, synthesis is

endergonic, meaning that glycogen is not synthesized without the input of energy. Energy
for glycogen synthesis comes from UTP, which reacts with glucose-1-phosphate, forming
UDP-glucose, in reaction catalysed by UDP-glucose pyrophosphorylase. Glycogen is
synthesized from monomers of UDP-glucose by the enzyme glycogen synthase, which
progressively lengthens the glycogen chain with (α1→4) bonded glucose. As glycogen
synthase can only lengthen an existing chain, the protein glycogenin is needed to initiate
the synthesis of glycogen. The glycogen-branching enzyme, amylo (α1→4) to (α1→6)
transglycosylase, catalyzes the transfer of a terminal fragment of 6-7 glucose residues
from a nonreducing end to the C-6 hydroxyl group of a glucose residue deeper into the
interior of the glycogen molecule. The branching enzyme can only act upon a branch
having at least 11 residues, and the enzyme may transfer to the same glucose chain or
adjacent glucose chains.

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Breakdown

Glycogen is cleaved from the nonreducing ends of the chain by the enzyme glycogen
phosphorylase to produce monomers of glucose-1-phosphate that is then converted to
glucose 6-phosphate. A special debranching enzyme is needed to remove the alpha(1-6)
branches in branched glycogen and reshape the chain into linear polymer. The G6P
monomers produced have three possible fates:

• G6P can continue on the glycolysis pathway and be used as fuel.

• G6P can enter the pentose phosphate pathway via the enzyme Glucose-6-
phosphate dehydrogenase to produce NADPH and 5-carbon sugars.
• In the liver and kidney, G6P can be dephosphorylated back to Glucose by the
enzyme Glucose 6-phosphatase. This is the final step in the gluconeogenesis
pathway.

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Glycogen debt and endurance exercise

Due to the body's inability to hold more than around 2,000 kcal of glycogen, long-
distance athletes such as marathon runners, cross-country skiers, and cyclists go into
glycogen debt, where almost all of the athlete's glycogen stores are depleted after long
periods of exertion without enough energy consumption. This phenomenon is referred to
as "hitting the wall". In marathon runners it normally happens around the 20 mile (32 km)
point of a marathon, where around 100 kcal are spent per mile,[citation needed] depending on
the size of the runner and the race course. However, it can be delayed by a carbohydrate
loading before the task.

When experiencing glycogen debt, athletes often experience extreme fatigue to the point
that it is difficult to move.

Disorders of glycogen metabolism

The most common disease in which glycogen metabolism becomes abnormal is diabetes,
in which, because of abnormal amounts of insulin, liver glycogen can be abnormally
accumulated or depleted. Restoration of normal glucose metabolism usually normalizes
glycogen metabolism as well.

In hypoglycemia caused by excessive insulin, liver glycogen levels are high, but the high
insulin level prevents the glycogenolysis necessary to maintain normal blood sugar
levels. Glucagon is a common treatment for this type of hypoglycemia.

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Various inborn errors of metabolism are caused by deficiencies of enzymes necessary for
glycogen synthesis or breakdown. These are collectively referred to as glycogen storage
diseases.

Why Glycogen as an Energy Storage Molecule?

1. Fat cannot be as rapidly mobilized in skeletal muscle.
2. Fat cannot be oxidized to produce energy in the absence of oxygen.
3. Energy input required to initiate fat oxidation.
4. The carbon atoms of fat cannot be used by any pathway of the human body in order to
maintain blood glucose levels for use by other tissues such as the brain. (i.e. fat cannot
be converted to glucose)

Reference

1. P. C. Calder (1991) Glycogen structure and biogenesis Int. J. Biochem. 23, 1335-
1352

2. Z. Gunja-Smith, J. J. Marshall, C. Mercier, E. E. Smith and W. J. Whelan (1971)

A revision of the Meyer–Bernfeld model of glycogen and amylopectin, FEBS Lett.
12, 101–104

3. E. Meléndez-Hevia, R. Meléndez and E. I. Canela (2000) Glycogen Structure: an

Evolutionary View, pp. 319–326 in Technological and Medical Implications of
Metabolic Control Analysis (ed. A. Cornish-Bowden and M. L. Cárdenas), Kluwer
Academic Publishers, Dordrecht

4.Carbohydrate Chemistry (Oxford Chemistry Primers, 99)

5. The sweet science of glycobiology: complex carbohydrates, molecules that are
particularly important for communication among cells, are coming under systematic ...
An article from: American Scientist

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