CHEM 201: BIOCHEMISTRY| LECTURE

BIOENERGETICS AND METABOLISM

FINALS | S.Y 2022 – 2023
MICHAEL DANN SUPERIO, MSc

OUTLINE ● Subjected to the laws of thermodynamics

I. Photosynthesis ○ Living organisms are open systems:
II. Metabolism and Energy: Bioenergetics exchanges matter and energy with the
A. Metabolic Pathways environment
B. Energy ● Bioenergetics
C. Laws of Thermodynamics ○ The study of how organisms manage
D. Laws of Thermodynamics:
energy resources via metabolic
Thermodynamic Quantities
E. Metabolic Reactions pathways
F. The Role of Oxidation and Reduction in
Metabolism A. METABOLIC PATHWAYS
G. Important Coenzymes in Metabolic ● Also known as biochemical pathways
Pathways ● Sequence of chemical reactions
H. Coupling of Production and Use of ● Product of one reaction serve as substrate for
Energy the next
● Metabolic pathways come in two forms:
BIOENERGETICS AND METABOLISM ○ Chain reaction
■ The end product is entirely
I. PHOTOSYNTHESIS
different from the starting
● Photosynthesis generates oxygen and glucose
reactant
which is then used by the cell to produce energy,
○ Cycle
water, and carbon dioxide.
■ The initial reactant undergoes a
series of chemical changes to
yield metabolites necessary for
other reactions and will
ultimately end up as a
compound similar to the initial
reactant
● Most pathways take place on specific regions of
the cells particularly the cytoplasm and
mitochondria

II. METABOLISM AND ENERGY: BIOENERGETICS

● Living cells generate thousand of different
reactions
● Sum of these reactions is known as metabolism,
the biochemical basis of all life processes
○ Failure among these reactions can
potentially lead to incorrect products or
cell death which in turn can affect the B. ENERGY
body dramatically ● Defined as the capacity to do work or cause
● Metabolism is divided into two pathways: change
○ Catabolism ● Comes in two general forms:
■ Breaking down of materials ○ Potential energy
○ Anabolism ■ Stored energy or potential to do
■ Building of structures works

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 ○ Kinetic energy
■ Energy in motion
● Can transfer into other forms of energy such as
mechanical, electrical, and heat depending on
what type of energy is needed in a particular
process
● Energy transformation is always governed by
laws of thermodynamics
C. LAWS OF THERMODYNAMICS
● Four Laws
○ Zeroth (0th) Law
○ First Law
■ Law of Conservation of
Energy
● Energy cannot be
created or destroyed,
but can only be
transformed from one
form to another
● Any form of energy is
not created, you can
only harness it from a
source
■ Illustration A
● The internal energy
(Delta U) of the system
is equal to the energy
used to do work, the
energy lost to heat, and
the total food energy
● This is true in any
consumer at a trophic
level. The total energy
we get from food is
transferred into the
energy we used to do
work into heat that is
emitted by the body
and leftover food
energy in the form of
fecal matter
■ Illustration B
● The inner energy is
transferred into
FERNANDEZ, J. & DEAPERA | 2F | 2 of 7
producers in a food
chain
● The total amount of
heat transferred from
the sun to the plant is
used to produce
glucose which is a form
of stored energy that
can be used by the
plant and consumers
■ If you consume the plant, you
can use the harnessed energy
by the plant for aerobic
respiration
○ Second Law
■ Entropy or Disorderliness
● For a spontaneous
process, the entropy
(disorderliness) will
always increase over
time
● Think of a well-ordered
room, and it will
become chaotic over
time by random
placement of things. It
can only become tidy
and orderly if you put
the effort and energy to
clean it and put the
things back in the right
places
● This is true in any
system, we get
disordered to live. From
a state of being orderly,
we spontaneously
become disordered and
to return to being
orderly, we need an
input of energy in the
form of material
consumption
● By analogy, if you do
not replace the energy
lost in the process of
becoming disorderly,
your body will not
become ordered, and
will become one with
the environment and
you will die. This is also
known as homeostasis.
● This cycle of
orderliness and
disorderliness is a
central concept of the
second law of
 thermodynamics and ● ΔG- total of free energy
this place why energy in the reaction
is essential to living ● ΔH- change in heat in
systems the reaction
● TΔS- product of the
temperature and
disorderliness of the
system or change in
entropy

E. METABOLIC REACTIONS

○ Third Law

D. LAWS OF THERMODYNAMICS: THERMODYNAMIC

QUANTITIES
● Thermodynamic quantities describe energy
changes occurring in a chemical reaction
○ Gibbs free energy (ΔG)
● Catabolism
■ Amount of energy capable of
○ The set of metabolic pathways that
work during reaction at constant
breaks down molecules into smaller
temperature and pressure
units that are either oxidized to release
● Inside the cells the
energy or used in other anabolic
temperature and
reactions
pressure is always
○ The Gibbs free energy in catabolism
constant unless acted
could be zero or negative
by an external force
● Anabolism
■ (+ΔG)
○ The set of metabolic pathways that
● Endergonic reaction;
construct molecules from smaller units,
system gains energy
these reactions require energy, known
■ (-ΔG)
also as an endergonic process
● Exergonic reaction;
○ The Gibbs free energy in anabolic
system releases
reactions are always positive
energy
○ Enthalpy (ΔH)
■ Heat content of a system
■ Reflects the number and kinds
of chemical bonds in the
reactants and products
■ (+ΔH)
● Endothermic; system
takes heat from
surrounding
■ (-ΔH) ● On the left side in the photo, the starting
● Exothermic; system materials of catabolism are huge
releases heat macromolecules
○ Entropy (S) ○ Through oxidative reaction:
■ Randomness or disorder in a ■ Fats -> Fatty acids and glycerol
system ■ Polysaccharides -> Glucose
■ ΔG = ΔH - TΔS and other monosaccharides
● Represents the total ■ Proteins -> Amino acids
energy in the reaction

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 ○ After broken down through oxidative
reaction, it will become small molecules
which can be used in anabolism
● Catabolic reactions are oxidative in nature
● Anabolism utilizes the materials and energy
from catabolic reactions and are reductive in
nature
F. THE ROLE OF OXIDATION AND REDUCTION IN
METABOLISM
● Oxidation-reduction reactions (aka redox
reactions) are central to metabolic pathways
● Oxidation
○ Loss of electrons or hydrogen or the
addition of oxygen into the compound
● Reduction
○ Addition of electron or hydrogen or the
loss of oxygen from the compound
● Oxidizing Agent
○ Substance that gains electron
● Reducing Agent
○ Substance that loses electron
● The reaction of zinc with aqueous copper and
aqueous zinc and a solid copper
○ Copper ions are dissolved in water
● Oxidation States
○ Numbers that are found on superscripts
on the end of the element
● Zn(s) + Cu²⁺ (aq) -> Zn²⁺(aq) + Cu(s)
○ Oxidation states (left side)
■ Zn- 0
■ Cu- 2+
○ Oxidation states (right side)
■ Zn- 2+
■ Cu- 0
● Zn -> Zn²⁺ + 2ℯ⁻
○ The zinc loses two electrons, hence 2ℯ⁻
● Cu²⁺ + 2ℯ⁻ -> Cu
○ Copper has 2+ and will gain electrons,
hence plus 2ℯ⁻ to yield the solid copper
● Zn -> Zn²⁺ + 2ℯ⁻ - Oxidation
Cu²⁺ + 2ℯ⁻ -> Cu - Reduction
_______________________
Zn + Cu² -> Zn² + Cu - Overall Reaction
● Taking into account the half reaction of zinc and
copper, we see that zinc loses two electrons and
copper gains two electrons. Basically the loss
electrons from zinc is transferred into the copper
hence, zinc underwent oxidation while copper
underwent reduction
● This reaction is particularly a clear example of
electron transfer and it will be useful to keep
these basic principles in mind when we examine
the flow of electrons in the more complex redox
reactions of aerobic metabolism
● In many biological redox reactions, the oxidation
state of carbon changes.
○ It will always be the oxidation state of
carbon because we are organic
organisms. We are carbon based, we
should always take into account the
oxidation state of carbon
● The figure shows the changes that occur as
carbon in its most reduced form which is the
alkane. It becomes oxidized into an alcohol into
an aldehyde and into a carboxylic acid and
ultimately into a carbon dioxide.
○ Each of these oxidations requires the
loss of two electrons catalyzed by
enzymes found in different parts of the
body.
G. IMPORTANT COENZYMES IN METABOLIC
PATHWAYS
● Coenzymes
○ Organic molecules that bind to active
sites of certain enzymes to assist in the
catalysis of a reaction, or be transferred
between enzymes as functional groups.
○ How do they assist?
■ Functions as intermediate
carriers of electron during the
reaction
○ Their main role in the catalysis of
reactions is their ability to hold and
transfer electrons from reactions
○ Unlike simple reactions like zinc and
copper in which the other reactant is the
electron receiver, most biological redox
reactions use coenzymes to carry
electrons so as to not destabilize the
structure of the product
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● Coenzyme A (CoA, CoASH)
○ Example of a reverse reaction of ethanol
to acetaldehyde that happens in the
liver.
○ The electron release is incapable of
binding to the aldehyde and has to go
somewhere, otherwise the free electrons
can wreak havoc in the system as a free
radical.
○ A coenzyme is necessary here to carry
these electrons to be delivered to
another metabolic pathway
● Nicotinamide Adenine Dinucleotide (NAD)
○ Example of a coenzyme
○ Oxidized = NAD+, Reduced = NADH
○ In the structure of NAD, the crucial
aspect in nicotine is the nicotinamide
part since they are the electron acceptor
○ Derived from Vitamin B3 or niacin,
making the vitamin an integral part of
our diet.
● Flavin Adenine Dinucleotide (FAD)
○ Another important coenzyme
○ Oxidized = FAD, Reduced = FADH2
○ Similar to NAD, the Flavin or riboflavin
part of the coenzyme is derived from
Vitamin B2 or riboflavin, making it
essential in diet
○ While both are electron carriers, NAD
and FAD. The difference between the
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two coenzymes is the point of delivery of
the electrons
○ Not an electron carrier, but is important
in the activation of metabolic pathways
■ Important in the oxidation of
pyruvate and synthesis of fatty
acids
○ The core vitamin of the structure
Coenzyme A is Vitamin B5 or
pantothenic acid
○ Unlike the two, NAD and FAD,
Coenzyme A is not an electron carrier
but is important in the activation of
metabolic pathways
○ Why is CoA a good example of
activation?
■ When bonded with a metabolite,
the free-energy change for
breaking the bond is negative
(-ΔG). This means, the ensuing
reaction is exergonic
■ A step frequently encountered
in metabolism is the process of
activation
■ In a reaction of this sort, a
metabolite, a component of a
metabolic pathway, is bonded
to some other molecule such as
coenzyme and the free-energy
change for breaking this new
bond is negative.
■ When we say Gibbs free-energy
which is negative, the next
reaction here so is exergonic
therefore, it will release energy
○ One of the most important points about
the multistep nature of all metabolic is
 that many stages allow for efficient
production and use of energy
○ By binding a metabolite with Coenzyme
A, the resulting product will have a
Gibbs free-energy with a negative value
meaning exergonic is energy rich and
that energy that is released by breaking
the CoA bond will then be used to
harness, to be used for another step of
metabolic activity
○ This is one example of such efficient
production and use of energy
● Coenzymes are important because without
electron transporter, oxidation of nutrients to
provide energy cannot take place
● Most, if not all, important biomolecules are
synthesized in organisms by many reactions in
which a metabolite is reduced while the reduced
form of a coenzyme is oxidized
● How is the energy released by the oxidation of
nutrients trapped and used?
○ The body will only release energy when
it is necessary. It will not randomly
release energy just for the sake of
releasing energy. It needs to be efficient
because it needs to conserve energy
○ Therefore, energy should only be
released when it is necessary
○ This energy cannot be used directly and
must be shunted into an easily
accessible form of chemical energy
H. COUPLING OF PRODUCTION AND USE OF
ENERGY
● Adenosine Triphosphate (ATP)
○ Energy currency of the cells
○ ATP is hydrolyzed (removal of
phosphate) to yield energy and ADP.
Conversely, phosphorylated of ADP to
produce ATP requires energy, which can
be supplied by the oxidation of nutrients
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○ The structure of this molecule is
relatively easy to break, especially on
the terminal phosphoric anhydride
linkage
■ The linkage between the
second and third phosphate
○ The energy rich phosphate upon
breaking releases 7.3 kilocalories per
mole
■ Enough to move proteins
across the cell membrane
○ Upon hydrolysis energy is released and
is harnessed by another system to
undergo chemical reaction
○ The energy released from the linkage
between the second and third phosphate
in the terminal phosphoric anhydride
linkage will be captured by another
chemical reaction to be used so that the
chemical reaction will take place
○ The product involved in this hydrolysis
are adenosine diphosphate (ADP) and
inorganic phosphate which participates
in the reformation of another energy
yielding molecule
○ There are also other energy currencies
in the cells, just replace adenosine with
the nitrogenous base that complements
it.
■ Could be guanine/guanosine or
uracil
○ Energy released from ATP hydrolysis is
immediately used in the target reaction.
 The consequential ADP is then recycled ○ In their reduced forms the same
to produce ATP coenzymes provide the reducing power
○ Cycling of ATP and ADP in metabolic needed for the anabolic processes of
processes is a way of shunting energy biosynthesis
from its production to its use when ○ Catabolism and Anabolism are
needed coupled together
■ By oxidation of nutrients to its ■ By exergonic reaction of
uses or processes such as catabolism, it releases energy
biosynthesis of essential which is then harnessed by
compounds or muscle anabolic processes to build the
contraction necessary structures in the
○ ATP hydrolysis is not stored energy body
○ ATP must be produced when they are ■ In between these two is ATP
needed which is the energy currency in
■ The body does not release the processes
energy randomly ● Aerobic Metabolism involves these series of
○ ATP hydrolysis generates the organism’s reactions to ensure that the organism lives
need for energy which takes place the
oxidation process
○ When chemical energy is stored it is
usually in the form of fats and
carbohydrates
■ Metabolized as needed
○ Certain biomolecules such as creatine
phosphate can also serve as vehicles for
storing chemical energy but it does not
last long
○ The energy must be supplied for the
many endergonic reactions in life
processes comes directly from ATP and
indirectly from oxidation of nutrients
■ Oxidation of nutrients produces
the energy needed for the
phosphorylation of ADP to ATP
● Coupling
○ The exergonic reaction of hydrolysis
provides energy, which in turn drives the
endergonic reaction.
○ Partnered release and use of energy on
chemical reactions
○ Since the products of catabolism is
utilized by anabolic processes, we can
say that these two are coupled together
○ The ATP produced by catabolism is
hydrolyzed to release the needed
energy
○ The reactions in which metabolites are
reduced are part of anabolism which
requires reducing agents such as
NADH, NADPH, or FADH2
■ NADPH = Phosphate attached
■ NADH = No phosphate
○ Usually NADPH is used for
photosynthesis and NADH for cellular
respiration
○ In their oxidized forms these coenzymes
serves as intermediate oxidizing agents
needed in catabolism

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 CHEM 301: BIOCHEMISTRY | LECTURE
CARBOHYDRATE METABOLISM
FINALS | S.Y 2022 – 2023
MICHAEL DANN SUPERIO, MSc

OUTLINE you chew, it becomes

I. Digestion of Carbohydrates more palatable.
A. Mouth to stomach - Only five percent of
B. Stomach to intestine starches are broken
C. Intestine to bloodstream down in the mouth.
II. Carbohydrate Metabolic Processes - This percentage is
A. Glucose Metabolic Processes
actually a good thing
B. Glycolysis
C. Possible Fates of Pyruvate in Glycolysis because as more
D. Pentose Phosphate Pathway glucose there is in the
E. GLYCOGENESIS mouth, the teeth are
F. GLYCOGENOLYSIS prone to decay. Thus,
G. GLYCONEOGENESIS it’s better that starch is
H. METABOLISM OF FRUCTOSE AND not all broken down.
GALACTOSE
Upon 20 rounds of
III. Conditions and Diseases Associated with
Carbohydrate Metabolism mastication, you
A. Examples of Conditions and Diseases swallow the food. Upon
Associated with Carbohydrate swallowing the food, it
Metabolism reaches the stomach.
From the stomach,
I. DIGESTION OF CARBOHYDRATES salivary amylase will no
● Pathway of carbohydrates from external source longer break down the
to inside the cells food because it does
A. MOUTH TO STOMACH not function well in the
● When we eat food, it enters our body through our
acidic conditions of the
mouth.
stomach.
● Mechanical and chemical digestion begins at the
- Once carbs reach
mouth
stomach, no further
○ Mastication (chewing): mechanical;
breakdown by
crumbles the carbohydrate food into
amylase
smaller and smaller pieces
- However, the
○ Enzyme action: chemical
mechanical breakdown
■ Salivary Amylase (contained by
is still ongoing. The
saliva)
strong peristaltic
- Breaks bonds
conditions of the
between the
stomach makes the
monomeric sugar
carbohydrates into a
units of
more uniform mixture
disaccharides,
of chyme. Chyme is a
oligosaccharides, and
mixture of partially
starches
digested food and
- Breaks down amylose
digestive juices.
and amylopectin into
dextrin and maltose
- The increased
concentration of
maltose in the mouth is
what enhances the
food’s sweetness. It’s
never very sweet, but
sweet at first bite. As

MAMALUBA & VARRON | 2F | 1 of 13


● The salivary glands in the oral cavity: parotid,
sublingual, and submandibular gland secrete
saliva that coats the food particles
Starch “POLY-alpha-D-GLUCOSE”
B. STOMACH TO INTESTINE
● Chyme reaches the upper part of the small
intestine; pancreatic amylase breaks down
dextrin into a shorter carbohydrate chain.
● Upon entry of the chyme into the intestinal
part of the digestive system, the pancreas
releases pancreatic juice through a duct. This
pancreatic juice contains the enzyme
pancreatic amylase which breaks down the
dextrin into shorter and shorter carbohydrate
chains. Additionally, enzymes are secreted by
intestinal cells that line the villi.
● Intestinal villi releases disaccharidases: sucrase,
maltase, lactase
○ Sucrase: sucrose → glucose +
fructose
○ Maltase: maltose → glucose +
glucose
○ Lactase: lactose → glucose +
galactose
● Once broken down into monosaccharides,
compounds are ready to enter the bloodstream
via facilitated diffusion in the intestinal villi
(fructose) and active transport (glucose and
galactose).
● When people do not have enough of the enzyme
lactase, lactose is not sufficiently broken down.
This results in a condition called lactose
intolerance. The undigested lactose moves to
the large intestine where bacteria are able to
digest it (bacterial lactase). The bacterial
indigestion of lactose produces gases leading to
symptoms of diarrhea, bloating, and abdominal
cramps. Lactose intolerance usually occurs in
adults and is associated by race. Most of
Caucasians, Africans, and East Asians
experience this.
C. INTESTINE TO BLOODSTREAM
● Molecular transport through intestinal villi
introduces monosaccharides into the
bloodstream.
● First organ to receive monosaccharides: liver
● Inside the liver, a number of enzymes do the
following within the hepatocytes:
○ Converts galactose to glucose
○ Breaks fructose into smaller
carbon-containing units
○ Stores glucose as glycogen or exports it
back to the blood
■ Controlled by hormones;
glucose regulates its own
concentration in the blood
Carbohydrate digestion begins in the mouth and is most
extensive in the small intestine. The resultant
monosaccharides are absorbed into the bloodstream and
transported to the liver.
II. CARBOHYDRATE METABOLIC PROCESSES
● How glucose is utilized by the body
● Despite the difference of cells, each has the
same metabolic pathway for each biomolecule.
A. GLUCOSE METABOLIC PROCESSES
● Glucose is utilized by numerous metabolic
pathways in the body; mostly, to yield energy
and metabolites which are precursors in the
formation of other biomolecules.
○ Glycolysis (catabolic activity)
○ Pentose Phosphate Pathway (catabolic
activity)
● Glucose, if there is too much in the bloodstream,
is stored in the liver and muscles (glycogenesis,
an anabolic activity). If there is a demand for
glucose in certain tissues, these stores are
utilized (glycogenolysis, a catabolic activity).
● Glucose can be sourced from non-carbohydrate
compounds by a series of metabolic pathways
(gluconeogenesis, an anabolic activity). The
body can produce glucose without the aid of
eating carbohydrates, but it will take more
energy.
B. GLYCOLYSIS
● First stage of glucose metabolism. Happens in
the cytoplasm of cells.
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● The main target of glycolysis: Glucose (6 REACTIONS INVOLVED IN GLYCOLYSIS
carbon-compound, or 6C) is split into two I. Phosphorylation Glucose + ATP →
pyruvate molecules (3C). Glucose-6-phosphate + ADP
● Involves a series of steps, each reaction II. Isomerization Glucose-6-phosphate →
catalyzed by an enzyme specific for that reaction. Reshuffling of the Fructose-6-phosphate
structure of the
● Uses ATP along the pathway as well as produces
reactant
ATP. By the endpoint of glycolysis, it also III. Phosphorylation Fructose-6-phosphate + ATP →
produces ATP. The ATP used is replenished Fructose-1,6-bisphosp Fructose-1,6-bisphosphate + ADP
by the end of the activity. hate is a very
● Divided into two phases: phosphorylation (or unstable molecule,
priming) phase (attachment of phosphate) thus, it breaks down
and energy-yielding phase (formation of ATP). immediately (see next
reaction)
● Phosphorylation: preparing phase of glucose
IV. Cleavage Fructose-1,6-bisphosphate →
molecule for yielding energy Not 2 molecules Glyceraldehyde-3-phosphate +
because of the Dihydroxyacetone phosphate
structure of
fructose-1,6-bisphosp
hate. It is an
asymmetrical
molecule and since
it’s unstable, it will
break fructose itself.
Fructose is a ketose,
thus, at least one of
the products should
be a ketone.
Dihydroxyacetone
phosphate is a
ketone, while
glyceraldehyde-3-pho
sphate is an aldose.
V. Isomerization Dihydroxyacetone phosphate →
Reshuffling of the Glyceraldehyde-3-phosphate
structure of the
reactant; there are
now 2 molecules of
glyceraldehyde-3-pho
sphate which will
● [Discussion of the picture above] The first five
enter the next part of
steps is the phosphorylation of glucose. the pathway.
Conversion of two molecules of VI. Oxidation (and Glyceraldehyde-3-phosphate +
glyceraldehyde-3-phosphate which utilizes 2 phosphorylation) NAD+ + Pi → NADH + 1,3-
ATPs to prime the reaction. Phase 2 is the The 2 molecules of bisphosphoglycerate + H+
conversion of glyceraldehyde-3-phosphate into glyceraldehyde-3-pho
pyruvate and coupled formation of four sphate receive an
inorganic phosphate
molecules of ATP.
that is free floating
● In all these reactions, the conversion of glucose around the cytoplasm
to product is an oxidation reaction, requiring an to yield NADH. NADH
accompanying reduction reaction in which NAD+ is the result of the
is converted to NADH. The breakdown of oxidation of NAD.
glucose to pyruvate can be summarized as VII. Transfer of a 1,3-bisphosphoglycerate + ADP →
follows: phosphate group 3-phosphoglycerate + ATP
The 2 phosphate
● Glucose (six carbon atoms) → 2 pyruvate
groups are attached
(each of which contains three carbon atoms) to the 1,3 of the
● 2ATP + 4ADP + 2P i → 2ADP + 4ATP glyceride molecule.
(Phosphorylation) One of these
● Glucose + 2ADP + 2Pi → 2 Pyruvate + 2ATP phosphate groups is
(Net reaction) cleaved and is
● Since there are 2 ATPs used to yield ADP, these received by ADP to
yield a free
2 ATPs are replenished by the 4 ATP.
phosphoglycerate +
ATP. There are

MAMALUBA & VARRON | 2F | 3 of 13

actually 2 VIII. Isomerization Phosphoglyceromutase
glyceraldehyde-3-pho IX. Dehydration Enolase
sphates that entered
this phase, thus, there X. Transfer of Pyruvate kinase
are also 2 phosphate group
1,3-bisphosphoglycer Overall Lactate dehydrogenase
ates. Therefore, there
must be also be 2
3-phosphoglycerate
and 2 ATP molecules.
VIII. Isomerization 3-phosphoglycerate →
Phosphate group is 2-phosphoglycerate
reshuffled to be
attached at the
second carbon rather
than the third.
IX. Dehydration 2-phosphoglycerate →
2-phosphoglycerate is phosphoenolpyruvate + H2O
dehydrated to
phosphoenolpyruvate,
yielding 2 molecules
of H2O. There are 2
2-phosphoglycerate *ΔG°´ values are assumed to be the same at 25°C and
and 2 37°C and are calculated for standard-state conditions (1
phosphoenolpyruvate M concentration of reactants and products pH 7.0).
s, thus, there must be **ΔG values are calculated at 310 K (37°C) using
2 water molecules as steady-state concentrations of these metabolites found in
well.
erythrocytes.
X. Transfer of Phosphoenolpyruvate + ADP →
phosphate group Pyruvate + ATP
An energy-yielding C. POSSIBLE FATES OF PYRUVATE IN GLYCOLYSIS
reaction. ● When pyruvate is formed, it can have one of
Phosphoenolpyruvate several fates:
releases its last ○ In the presence of oxygen (aerobic
phosphate group to metabolism), pyruvate loses CO2, the
be received by ADP to remaining 2C compound is linked to
yield pyruvate and coenzyme A to form acetylCoA which
ATP.
enters the citric acid cycle (Krebs Cycle)
○ Pyruvate contains 3 carbons, it loses
● The main product in each reaction, they are the
one carbon through carbon dioxide
ones used as reactant in the next reaction.
decarboxylation.
● The first five reactions in glycolysis is the priming
○ In the absence of oxygen (anaerobic
phase; the last five involves the energy-yielding
metabolism), pyruvate loses CO2 to
phase.
produce acetaldehyde which is reduced
● All of the reactions above are used to yield
to ethanol (fermentation) or pyruvate is
energy.
reduced to lactate to produce lactic acid
(anaerobic glycolysis, happens in
ENZYMES INVOLVED IN GLYCOLYSIS
mammals especially in muscle tissues; if
I. Phosphorylation Hexokinase (generalist enzyme
which catalyzes the attachment of you are not taking in enough oxygen in
phosphate in any hexose your body while doing a strenuous
molecule) /glucokinase (found in activity, lactic acid will accumulate;
the liver) pyruvate will enter anaerobic glycolysis
II. Isomerization Glucose phosphate isomerase (for to produce lactic acid which will
the isomerization) accumulate in muscles = pamaol).
III. Phosphorylation Phosphofructokinase (to attach ○ Stretch out the sore muscles and utilize
another phosphate)
lactic acid. Lactic acid will be
IV. Cleavage Aldolase
transformed back into pyruvate to enter
V. Isomerization Triose phosphate isomerase
the acetic acid cycle until the soreness is
VI. Oxidation (and Glyceraldehyde-3-P gone.
phosphorylation) dehydrogenase
○ In all these reactions, conversion of
VII. Transfer of a Phosphoglycerate kinase
phosphate group glucose to product is an oxidation
reaction.

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 ● Glucose-6-phosphate is prepped by hexokinase
by glucokinase by attaching a phosphate group
from ATP to glucose.
● The pentose phosphate pathway begins with a
series of oxidation reactions that produce
NADPH and five carbon sugars. The remainder
of the pathway involves non-oxidative reshuffling
of the carbon skeletons of the sugars involved.
● The products of these non-oxidative reactions
include substances such as
fructose-6-phosphate and
glyceraldehyde-3-phosphate which play a role in
the glycolysis. These products can enter the
glycolytic pathway since they are in the
cytoplasm.
● In the first reaction of the pentose phosphate
pathway, glucose-6-phosphate is oxidized to
[An illustration of the fate of pyruvate upon being formed 6-phosphogluconate by NADP+. Removal of
after glycolysis] hydrogen involves oxidation. NADPH is a form of
One molecule of glucose is converted to two molecules of energy coupling, so the energy released is used
pyruvate. Under aerobic conditions, pyruvate is oxidized in reductive anabolic pathways. The enzyme
to CO2 and H2O by the citric acid cycle and oxidative that catalyzed the first reaction is
phosphorylation. Under anaerobic conditions, lactate is glucose-6-phosphate dehydrogenase. This
produced, especially in muscle. Alcoholic fermentation enzyme cleaves the hydrogen in the upper right
occurs in yeast. The NADH produced in the conversion of and attaches an oxygen from H2O and the
glucose to pyruvate is reoxidized to NAD+ in the hydrogen in the NADPH is used in reductive
subsequent reactions of pyruvate. anabolic pathways.
● The next reaction is an oxidative decarboxylation
D. PENTOSE PHOSPHATE PATHWAY (removal of carbon dioxide). NADPH is produced
● Alternative pathway to glycolysis; crux is not again. The 6-phosphogluconate molecule loses
the production of energy. its carboxyl group released as carbon dioxide.
● Important for the production of pentoses (5C The 5-carbon keto sugar ribulose-5-phosphate is
sugars) including ribose essential in the the other product. The enzyme that catalyzes
formation of nucleic acids. this reaction is 6-phosphogluconate
● Glucose, which is a 6C molecule, is used as dehydrogenase. In the process, the carbon 3
the main reactant to produce 5C sugars hydroxyl group of the 6-phosphogluconate is
(ribose). oxidized to form an R keto acid which is unstable
● Also important in the production of and readily decarboxylates to form
nicotinamide adenine dinucleotide phosphate ribulose-5-phosphate. The OH group is removed.
(NADPH), a coenzyme critical in the Upon removal, the molecule decarboxylyzes
biosynthesis of lipids. immediately without the assistance of
● Therefore, glucose (carbohydrate) is essential enzymes because of instability.
for generating the DNA and RNA.

[Discussion of the illustration above]

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The structure of reduced adenine dinucleotide phosphate fructose-6-phosphate (12 C) and 1 molecule of
(NADPH). glyceraldehyde-3-phosphate (3 C) = 15 carbons.
● Only rearrangement of structure happens.
● The two molecules can now enter glycolysis.
● Therefore, the pentose phosphate pathway
can give intermediates for the glycolytic
pathway.
● The total number of carbon atoms does not
change, but there is a considerable
rearrangement as a result of group transfer. Two
enzymes, transketolase and transaldolase, are
responsible for the reshuffling of the carbon
atoms of sugar such as the ribose-5-phosphate
and xylulose-5-phosphate in the remainder of the
pathway, which consists of three reactions.
● The pentose phosphate pathway is important
in the production of ribose-5-phosphate
essential for nucleic acids and it could also
yield intermediates for the glycolysis. Thus,
[Discussion of illustration above] the end products are not wasted.
● In the remaining steps of the pentose Rearrangement of the structures of the
phosphate pathway, several reactions involve molecules can give intermediates or
transfer of two and three carbon units. To metabolites which can be used for glycolysis.
keep track of the carbon backbone of the sugars
and their aldehyde and ketone functional groups, E. GLYCOGENESIS
the formulas are written in their open chain
form.
● There are two reactions in which
ribulose-5-phosphate isomerizes. One of these
reactions is catalyzed by
phosphopentose-3-epimerase, yielding
xylulose-5-phosphate. The other reaction
catalyzed by phosphopentose isomerase
produces a sugar with an aldehyde group rather
than a ketone. Ribulose-5-phosphate
isomerizes to ribose-5-phosphate in the
second reaction (above). Ribose-5-phosphate
is a necessary building block for the
synthesis of nucleic acids and coenzymes
● Formation of glycogen from excessive
such as NADH. RIbose-5-phosphate is a
glucose in the bloodstream.
molecule that can be utilized to synthesize
● Synthesis requires energy (anabolic) from
DNA or RNA.
uridine triphosphate (UTP). Glucose is
● The group transfer reactions that link the pentose
activated to become uridine disphosphate
phosphate pathway with glycolysis require the
glucose, which is the primary form needed to
two 5C sugars produced by the isomerization of
synthesize glycogen.
ribulose-5-phosphate (ribose-5-phosphate &
The branched-chain structure of glycogen. The highly
xylulose-5-phosphate).
branched structure of glycogen makes it possible for
● Two molecules of xylulose-5-phosphate and one
several glucose residues to be released at once to meet
molecule of ribose-5-phosphate rearrange to give
energy needs. This would not be possible with a linear
two molecules of fructose-6-phosphate.
polymer. The red dots indicate the terminal glucose
● 3 molecules of pentose give two molecules of
residues that are released from glycogen. The more
hexoses and one molecule of triose.
branch points there are, the more of these terminal
● The end reaction of the rearrangement is a
residues are available at one time.
fructose-6-phosphate and a molecule of
● This would not be possible with a linear
glyceraldehyde-3 phosphate.
polymer because if its linear the
● 2 xylulose (10C) + 1 Ribose (5C) = 15 carbons
glucose residue must be at the
rearrange to yield 2 molecules of
terminal end of the structure to be

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 release. So, If terminal branches, there
are multiple terminals and if thereare
multiple terminals there are multiple
glucose.
1. Glycogen synthesis is primed by glycogenin, a protein
that acts as core of a glycogen molecule.
● Glycogenin - glycogen protein core. It catalyzes
the initial step in the formation of glycogen.
● Autocatalysis - Glycogen itself serves as a
catalyst
● Glucose is activated by uridine triphosphate.
One phosphate molecule is release and glucose
is attaches to it and become UDP glucose is
catalyzed.
2. Glucose-6-phosphate reacts with UTP to yield
UDP-glucose. UDPG transfers glucose (autocatalyzed) to
a specific tyrosyl group of glucogenin.
● Tyrosyl group is replace by glycosyl unit
● Glucose UDPG release the glucose part relieving
UDP or UTP is replenished by simple transfer of
phosphate from ATP to UDP to yield another
form of UDP.
3. Continuous addition of UDPG to a growing chain. Each
step involves formation of a new α(1→4) glycosidic
linkage
4. At about eighth glucose residue, glycogen synthase
takes over in catalyzing the synthesis of glycogen.
● This is because the terminal end of glucose
molecule is now too far from glycogenin and it
can longer catalyzed because of the length of the
chain. So glycogen synthase take over to
synthesize glycogen.
5. At about 12th residue, a branching enzyme catalyzes
the attachment of a glucose oligosaccharide through an
α(1→6) glycosidic linkage. Each branch must be at least
4 residues away from the nearest existing branch point
6. Glycogen synthase and branching enzymes continue
to add glucose until glycogen molecules become mature.
● At about 60000 glucosil units
● This is specific for each molecule of glycogen.
Imagine the molecular weight of glycogen
contains about 60000 plus the molecular weight
of glycogenin
F. GLYCOGENOLYSIS
Note: Involves the breakdown of glycogen if there is a
need for immediate release of glucose into the blood
stream or certain cases into the cytoplasm of muscle
cells.
● Glycogen is found primarily in the liver and
muscles.
● Release of liver glycogen store is triggered by
low blood glucose levels. Liver glycogen is
broken down to glucose-6- phosphate, which is
hydrolyzed to give glucose. This replenishes
blood glucose levels.
● Release of muscle glycogen store is triggered by
low cytoplasmic glucose levels, such as during
intense exercise. Glucose-6-phosphate enters
the glycolytic pathway directly rather than being
exported to the bloodstream.
○ In muscles however glucose
6-phosphate obtained from glycogen
breakdown enters the glycolytic pathway
directly rather than being hydrolyzed to
glucose and then exporated to the
bloodstream.
○ Difference between glucose release
from the liver and muscles.
○ For liver - glycogen is released into
the bloodstream.
○ Muscles - Muscle glycogen releases
glucose to be utilized immediately by
the sarcoplasm of the muscles. This
is during intense workout.
● Note: There are three reactions that play role in
the conversion of glycogen in glucose 9
phosphate
● In the first reaction, each glucose residue
cleaved from glycogen reacts to phosphate to
give a glucose 1 phospahate. Note particularly,
this reaction is phosphorolysis reaction rather
hydrolysis. It does not use water to cleave but
uses phosphate ion and the enzyme
responsible to this reaction is
glycogenphosphorylase.
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 branch of free glucose residue to the
end of (around 57 mins) another branch
where there are subsequently removed
by glycogen phosphorylase.
○ Note:
■ glycogenesis - formation of
glucose
■ Glycogenolysis is the release if
glucose molecule from existing
glycogen stores.
■ Body is so traffic even when we
● In the second reaction glucose one phosphate is breathe.
iozomerized to give glucose six phosphate which G. GLYCONEOGENESIS
is now readily available to enter glycolysis. The
enzyme resposonsible for the isomerization of ● The conversion of pyruvate (and precursors)
glucose one phosphate is phosphogluco to glucose. Not the reverse of glycolysis.
mutase. ● Pyruvate can arise from other sources such
● Note: Glucose phosphorylase acts only on aslactate, glycerol (from triglycerides), alanine,
α(1→4) glycosidic linkages along the chain. and glutamine (amino acids).
For complete breakdown, debranching enzymes ○
degrade the α(1→6) glycosidic linkages. ● Oxaloacetate is an important intermediate
○ These are branches that form alpha between citric acid cycle (Krebs cycle) and
(1→6) glycosidic bond. gluconeogenesis
○ So, the formation of glycogen you have ○ Oxaloacetate can be converted to
branching enzymes and to release the pyruvate
(1→6) glycosidic linkage. It is now acted ■ Which can be used to be
upon by debranching enzymes converted to become glucose
○ Summary : glycogen phosphorylase which can now enter the
cleaves α(1→4) linkages in glycogen glycolytic pathway
complete breakdown requires the ○ All intermediates of the Krebs cycle can
branching enzymes to degrade that be converted to oxaloacetate
(1→6) linkages and note that no ATP is
hydrolyzed in the first reaction. No
energy is yielded.
○ In the glycolytic pathway we saw
another example of phosphorylation also
substrate directly by phosphate without
involnebt if ATP. This was the
phosphorylation of glyceraldehhyde free
phosphate (1→3) biphosphoglycerate.
This is an alternative mode of entry to
the glycolytic pathway that saves one
molecule of ATP for each molecule of
glucose because it bypasses the first
step in glycolysis
○ When glycogen rather than glucose is
the starting material for glycolysis there
is actually a net gain of 380 ATP
● Again, gluconeogenesis is not the reverse of
molecule for each glucose monomer
glycolysis.
rather than the two ATP molecules as
○ It is because if it is reversible then along
when glucose itself is the starting point.
the glycolytic pathway pyyruvate can be
○ Thus, glycogen is a more effective
immediately transformed to glucose
energy source than glucose.
because of reversible reactions
○ Ofcourse, there is no free lunch in
● Glycolysis has three irreversible steps, and
Biochemistry and as we shall see it
the difference between glycolysis and
takes energy to put glucoses together
gluconeogenesis lies within these reactions.
into glycogen. The debranching of
○ Production of pyruvate from
glycogen involves sa transfer of a limit
phosphoenolpyruvate

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 ■ Involves a release of
phosphate.
○ Production of fructose-1,6-bisphosphate
from fructose-6-phosphate
■ Another phosphorylation
reaction
○ Production of glucose-6-phosphate from
glucose
Note: These reactions or steps involves the attachment of
phosphate from ATP. However the other two reactions in
which gluconeogenesis differs from glycolysis are ones in
which a phosphate ester bond to a sugar hydroxyl group
is hydrolyzed. Both reactions are catalyzed by
phosphatases and most reactions are exergonic.
The reverse of these reaction is endergonic with reactions
two and three are required during production of ATP from
ADP. ○ In the last reaction in the release of
phosphate from phosphoenolpyruvate to
● Reverse of three reactions is endergonic with yield pyruvate. You can see here that
reactions 2 and 3 requiring production of ATP oyruvate can be transformed to
from ADP. oxaloacetate to enter the Kreb’s Cycle.
Oxaloacetate can be reversed by the
Non-carbohydrate sources of glucose addition of GTP and the assistance of
phosphoenolpyruvate carboxykinase to
become a phosphoenolpyruvate.
Pyruvate cannot be reversed back to
phosphoenolpyruvate by simply
attaching a phosphate group from ATP,
but it needs to become Oxaloacetate
first. Acetyl-CoA biotin pyruvate
carboxylase should be pyruvate
carboxylase and then oxaloacetate can
now be use to become
phosphoenolpyruvate by the action of
phosphoenolpyruvate carboxylkinase.
However, it is just pyrucate must first
enter the mitochondria.

● Pyruvate carboxylase catalyzes a

compartmentalized reaction. Pyruvate is
converted to oxaloacetate in the mitochondria.
Because oxaloacetate cannot be transported
across the mitochondrial membrane, it must be
reduced to malate, transported to the cytosol,
and then oxidized back to oxaloacetate before
gluconeogenesis can continue.
○ Glycosis happen in the cytoplasm. So,
pyruvate must first and enter the
● The first box on top is the third reaction. The mitochondrion so it becomes
production of glucose-6-phosphate from glucose. oxaloacetate. Pyruvate becomes
○ oxaloacetate through the action of
● The second box is the second reaction. The pyruvate carboxylase. Pyruvate
Production of fructose -1,6-bisphosphate from carboxylase upon being turned into
fructose-6-phosphate oxaloacetate it is reduced to become
● The third box is the first reaction Production of malate, after that malate exits the
pyruvate from phosphoenolpyruvate mitochondria.
○ Why needed to converted oxaloacetate
to malate?

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 ■ It is because oxaloacetate gluconeogenesis only involves non-carbohydrate source
cannot exit mitochondria. As te since fructose and galactose are carbohydrate they do
mitochondria does not have the not have the same pathway as with gluconeogenesis, but
necessary channels or transport a separate one.
molecules to transport
oxaloacetate from inside the
mitochondria to the cytoplasm.
But mallate has those transport
channels.
■ Oxaloacetate transformed into
malate by reduction reaction,
addition of hydrogen then
malate now exits and oxidized
(gitanggalan ng hydrogen) to
form oxaloacetate.
■ Oxaloacetate now become
phosphoenolpyruvate and
phosphoenolpyruvate can be
reverted back, can now enter
the glucogenesis pathway.
■ phosphoenolpyruvate becomes
phosphoglycerate three
phosphorus (1:08:01)
■ Upon transforming
glyceradehyde and dihydroxy
acetone can be reverted back to
fructose - 1,6 biphosphate,
■ However, fructose - 1,6
biphosphate, cannot be
immediately reverted back to
fructose six biphosphate. So an
enzyme fructose - 1,6
bisphosphatase catalyzes
this reaction by removing
phosphate group from the
anomeric carbon from the H. METABOLISM OF FRUCTOSE AND
carbon 1 of yourfructose GALACTOSE
yielding a fructose - 6 ● Fructose, upon reaching the liver, undergoes
phosphate plus phosphate fructolysis. Almost all fructose is used to
ion. replenish glycogen stores in the liver, whereas a
■ Now, it is fructose - 6 small portion is converted to triglycerides.
phosphate. It can now return ○ Fructose is catalyzed in the liver called
back to its glucose 6 phosphate fructolysis.
form and glucose 6 phosphate ● Galactose, on the other hand, undergoes the
can na become glucose by the Leloir pathway to become glucose-6-phosphate
action of glucose 6 ○ Glucose-6-phosphate can enter the
phosphatase and you have glycolytic pathway and since fructose is
these glucose molecule. used to replenish glycogen stores upon
■ How these molecule utilized by glycogenolysis. It now enter the
these cells is depending the glycolytic pathway to yield energy as
demand of the cells. It could well.
reenter the glycolytic pathway
or it could enter the pentose
phosphate pathway.
Note: That is what we call gluconeogenesis, it is parallel
to the glycolytic pathway or glycolysis, but it is not the
opposite of that particular pathway. Other sources of
glucose are fructose and galactose. Remember that

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 glucose one phosphate and ultimatelt it
will be reaction with UDP, UTP (uridine
trophosphate) UDP and then attached to
the glycogen inside the liver to become
glycogen or glucose 6 phosphate can
enter the phosphate pentose phosphate
pathway.

The metabolic conversion of fructose to DHAP,

glyceraldehyde andglyceraldehyde
-3-Phosphate in the liver

● Fructose upon the action of

fructokinase becomes fructose 1
phosphate.
● Fructose - 1, 6 phosphate is split into
glyceradehyde by aldolase and into
The metabolic conversion of fructose to
hydroxyl acetone phosphate. This
triglyceride (TG) in the liver
should be glyceradehyde 3 phosphate to
● After being transformed into
enter the glycolytic pathway pero
glyceraldehyde 3 phosphate it enters the
glyceraldehyde ra siya because this is
glycotic pathway to yieldm
fructose 1 phosphate not fructose 6
pyruvate.After that pyruvate kinas
phosphate.
become pyruvate. Pyruvate now enter
● Glyceraldehyde becomes
sthe Krebs Cycle to yield acetyl CoA
glyceradehyde 3 phosphate by the
enzyme. acetyl CoA enzyme before
action of triokinase and this is non
being utilized by the Kreb’s Cycle its
reversible.
shuffled outside the mitochondria to
● Dihydroxyacetone phosphate is
become fatty acids though the process
converted into glyceradehyde 3
of Lenovo lipogenesis or dihydroxyacetyl
phosphate by action of triokinase
phosphate DHAP is acted upon glycerol
isomerase. Since, it is now
3 phosphate dehydrogenase to yield
glyceradehyde 3 phosphate, it can now
glycerol 3 phosphate. G3P can be upon
enter the glycolytic pathway or again
esterification can yield to triglyceride.
since it is inside the liver, it now
● Obese people have fatty liver because
enters the glycogenetic and glycide
most of the glycogen stores as well as
like the glycogenesis pathway.
the conversion of fructose and
conversion of fructose to glycogen and
fats primarily happen in the liver.

● So, as you can see here is just an

expansion of the first chart.
The metabolic conversion of fructose to glycogen
in the liver
● Now that it is G3p it can be reformed to
fructose - 1, 6 biphospahet by aldolase
two becomes glucose 6- phosphate and
then following that mutase to become

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 ● This is an illustration on how galactose
from milk and fructose from sugar. From
fruits enters the glycolytic pathway here.
III. Conditions and Diseases Associated with
Carbohydrate Metabolism
What happens to the body if there are problems in the
metabolism of carbohydrates

● Carbohydrate metabolism disorders are a group

of metabolic disorders.
○ Can be caused by dysfunctional enzyme
structure or is caused by reduced
sensitivity to certain hormones.
■ Since enzymes are proteins and
proteins are in the blueprint of
proteins are inside the DNA
they can be genetic. So,
dysfunctional enzyme are
considered to be genetic or
cause by reduced sensitivity to
a certain hormones.
1. galactose mutarotase facilitates the ● Most of these disorders are inherited
conversion of β-Dgalactose to α-D-galactose ● Genetic tests on infants can be done using blood
since this is the active form in the pathway. tests
2. α-D-galactose is phosphorylated by
galactokinase to galactose-1-phosphate
3. galactose-1-phosphate uridylyltransferase A. Examples of Conditions and Diseases
converts galactose 1-phosphate to Associated with Carbohydrate Metabolism
UDP-galactose using UDPglucose as the uridine
diphosphate source
Disorder Definition
4. UDP-galactose 4-epimerase recycles the
UDP-galactose to UDP-glucose for the Diabetes Condition in which blood glucose
transferase reaction Mellitus levels are too high due to absence
5. UDP-glucose can now enter the glycogenesis (or low levels) of insulin or
cycle or phosphoglucomutase converts the insensitivity to the hormone.
D-glucose 1-phosphate to ● Two types:
D-glucose-6-phosphate and enter glycolysis’ ○ Type 1 - genetic
○ Type 2 - acquired
● The more you eat the more activity
and that is caused
happens inside your liver. Remember by stagnant
that liver is the organ first receives all lifestyle.
anything that you eat including medicine.
Most of the metabolic activities in your Galactosemia Inherited disorder that prevents the
digestive assistant begins at the liver. processing of galactose, resulting
to the build up of the compound
and can cause serious
Intermediates and enzymes in the Leloir pathway
complications in the body.
of galactose metabolism
Type I Glycogen Aka Von Gierke’s disease, it affects
Storage Disease the ability of the body to release
glucose from glycogen stores, with
affected people prone to
hypoglycemia.

Pompe Disease Rare, inherited, and often fatal

disorder that disables heart and
skeletal muscles caused by
mutations in the gene that produce
acid alpha glucosidase, an enzyme
similar to a debranching enzyme,
but in muscle cells.
● AAG is an enzyme similar

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to a deprenging enzyme
the branching enzyme
especially in the liver.
These cleaves glucose 6
phosphate from the
terminal ends of glycogen.
However, acid Alpha
glucosidase is found in the
muscles and in the heart. If
there is no continuous
source of glucose in the
heart and the muscles, it
would weak a person and
since there is no
continuous supply of
glucose on the heart
therefore there is a high
possibility that the cardiac
activity is lowered, the
resulting to heart failure
and myocardial infarction.
That is why Pompe
disease is a very fatal
disorder.

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