Biochemis

try
Prof: Rychie Kevin Membrado, RPh
 INTRODUCTION TO
BIOCHEMISTRY
Biochemistry is becoming one of the most influential areas of science.
Combining the core tenets of biology and chemistry, the field plays a huge role
in the study of majority of the medical and allied health sciences programs. By
definition, Biochemistry is the study of the chemical substances found in
living organisms and the Chemical interactions of these substances with each
other. A biochemical substance is a chemical substance found within a living
organism. Biochemical substances are divided into two groups: bioinorganic
(include water and inorganic salts) substances and bioorganic (include
carbohydrates, lipids, proteins, and nucleic acids). (Stoker, 3rd Ed.)

Considering all the rapidly expanding application, biochemistry is clearly far

from a single, monolithic discipline. From the mere study of the structures,
functions and interactions of biological macromolecules, biochemistry has
vastly contributed to various scientific inquiries. Medicine is just one area that
has benefited from it. It is vital in cell biology, physiology, pathology,
pharmacology, microbiology, immunology, nutrition, forensic medicine, and
toxicology, as well as the fields of inflammation, cell injury, and cancer. Aside
from these, biochemical research is also applied in industry, agriculture and
food production.
Biochemistry and medicine enjoy a mutually cooperative relationship. These
close relationships emphasize that life, as we know it, depends on biochemical
reactions, metabolism, functions and growth of a healthy human body.
In physiology, the study of body change in the biochemical processes
function, biochemistry has broadened taking place in the body. As such,
our understanding of how biochemical pharmacologists must also be
changes relate to physiological acquainted with the biochemical
alteration in the body. It helps us aspects of the human body. In
understand the chemical aspects of pharmacy, biochemical testing
biological processes such as digestion, provides indispensable insights into a
hormonal action, and other metabolic drug’s: mode of action, half-life, and
dysfunction, etc. storage conditions, metabolism, and
potential toxic or adverse effects.
Biochemistry is also the sole field that
In pathology, biochemical studies
accurately describes the function and
have illuminated many aspects of
role of vitamins in the body. With
health and disease. The study of how
millions of people taking daily
aberrant biochemistry relates to
vitamins and mineral supplements, the
disease conditions in the human body,
ongoing discoveries made my
physicians can use biochemical
biochemists will continue to exert a
analysis to confirm diagnosis based on
huge impact on the field of nutritional
patient testimony. Such in the critical
deficiency. As with the subfields of
determination of the occurrence of
biochemistry in genomics, it is
diabetes, hypercholesterolemia, hypo-
carrying a long-term implication for
and hyperthyroidism, jaundice, kidney
drug development and other clinical
dysfunction, sickle cell anemia,
workflows. Genome sequencing, for
marasmus, rickets, lysosomal storage
example, is causing a ‘revolution’ in
diseases, collagenopathies,
early diagnosis and determination of
atherosclerosis and etc. With
hereditary diseases — a breakthrough
information gleaned from the
that could fast-track the development
chemical nature of pathologies,
of vital new treatments for a range of
laboratory investigations, analysis and
health conditions.
studies are able to investigate potential
treatments for diseases. The action of
a drug almost always involves some
Undeniably, our appreciation of
biochemistry as we integrate scientific
With the modules prepared, we
knowledge of the chemical processes
encourage you to take time reading
in living cells paved the way to our
and understanding the details of the
practical strategies to maintain health,
content. We wish you an exciting self-
understand disease, identify potential
discovered independent learning
therapies, and enhance our
experience with biochemistry. And,
understanding of the origins of life on
we do hope that you will consider
earth.
these pieces as a keepsake.

CARBOHYDRATES
INTRODUCTION
Carbohydrates are the most abundant class of bioorganic molecules on planet
Earth. Although their abundance in the human body is relatively low,
carbohydrates constitute about 75% by mass of dry plant materials. Green
(chlorophyll- containing) plants produce carbohydrates via photosynthesis. In
this process, carbon dioxide from the air and water from the soil are the
reactants, and sunlight absorbed by chlorophyll is the energy source.
Chlorophyll
CO2 + H2O + solar energy------Carbohydrates
Plant enzyme

Plants have two main uses for the carbohydrates they produce. In the form of
cellulose, carbohydrates serve as structural elements, and in the form of starch,
they provide energy reserves for the plants. Dietary intake of plant materials is
the major carbohydrate source for humans and animals. The average human
diet should ideally be about two-thirds carbohydrate by mass.

Carbohydrates have the following functions in humans:

1. Carbohydrate oxidation provides energy.
2. Carbohydrate storage, in the form of glycogen, provides a short-term energy
reserve
3. Carbohydrates supply carbon atoms for the synthesis of other biochemical
substances (proteins, lipids, and nucleic acids).
4. Carbohydrates form part of the structural framework of DNA and RNA
molecules.
5. Carbohydrates linked to lipids are structural components of cell membranes.
6. Carbohydrates linked to proteins function in a variety of cell–cell and cell–
molecule recognition processes.
In this module you will learn how carbohydrates are formed through structural
arrangement, the classification and the uses of the different sugars or
carbohydrates. This entails you to review basic organic chemistry (refer to the
table of functional group).

Main Lesson:
Activity 2: Content notes (70 min).
Instructions: Please highlight the
MOST important information.
Note, it will help if you check the
skill building activity first.
A carbohydrate (Cn(H2O)n) is a polyhydroxy aldehyde, a polyhydroxy ketone,
or a compound that yields polyhydroxy aldehydes or polyhydroxy ketones
upon hydrolysis. The carbohydrate glucose is a polyhydroxy aldehyde, and the
carbohydrate fructose is a polyhydroxy ketone.

Classification of carbohydrates
UNDERSTANDING PRINCIPLES ON
THE MOLECULAR STRUCTURES OF
CARBOHYDRATES
The structures of carbohydrates are far from for being basic and ordinary.
However, through the delicate principles involves from chirality-the
handedness in molecules to Haworth projection formulas, details as to how
sugars looks and linked together can be understood in simple yet challenging
ways.
Mirror images
First, an important property of many
molecules, including most carbohydrates, is
“handedness,” which is a form of isomerism.
Molecules that possess “handedness” exist in two
forms: a “left-handed” form and a “right- handed”
form. These two forms are related to each other in
the same way that a pair of hands is related to each
other. The relationship is that of mirror images. A
left hand and a right hand are mirror images of each
other. Objects can be divided into two classes on
the basis of their mirror images: objects with
superimposable mirror images and objects with
nonsuperimposable mirror images.
Superimposable mirror images are images that coincide at all points when the
images are laid upon each other. Nonsuperimposable mirror images are
images where not all points coincide when the images are laid upon each
other.

Chirality
Some, but not all, molecules possess handedness. What determines
whether or not a molecule possesses handedness is the presence of a carbon
atom that has four different groups bonded to it in a tetrahedral orientation.
The tetrahedral orientation requirement is met only if the bonds to the four
different groups are all single bonds. The handedness-generating carbon atom
is called a chiral center. A chiral center is an atom in a molecule that has four
different groups bonded to it in a tetrahedral orientation. A molecule that
contains a chiral center is said to be chiral. A chiral molecule is a molecule
whose mirror images are not superimposable. Chiral molecules have
handedness. An achiral molecule is a molecule whose mirror images are
superimposable. Achiral molecules do not possess handedness.
The Importance of Chirality
In human body chemistry, right-handed and left-handed forms of a molecule
often elicit different responses within the body. Sometimes both forms are
biologically active, each form giving a different
response; sometimes both elicit the same response, but one form’s response is
many times greater than that of the other; and sometimes only one of the two
forms is biochemically active. For example, studies show that the body’s
response to the right-handed form of the hormone epinephrine is 20 times
greater than its response to the left-handed form.

Monosaccharides, the simplest type of carbohydrate and the building block for
more complex types of carbohydrates, are almost always “right-handed.”
Plants, the main dietary source of carbohydrates, produce only right-handed
monosaccharides. Interestingly, the building blocks for proteins, amino acids,
are always left-handed molecules.

STEREOISOMERISM: ENANTIOMERS
and DIASTEREOMERS
The left- and right-handed forms of a chiral molecule are isomers. They
are not constitutional isomers, but rather are stereoisomers. Stereoisomers are
isomers that have the same molecular and structural formulas but differ in the
orientation of atoms in space. By contrast, atoms are connected to each other
in different ways in constitutional isomers.
Stereoisomers can be subdivided into two types: enantiomers and
diastereomers. Enantiomers (Enantios- means opposite) are stereoisomers
whose molecules are nonsuperimposable mirror images of each other. Left-
and right-handed forms of a molecule with a single chiral center are
enantiomers. Diastereomers are stereoisomers whose molecules are not mirror
images of each other. Cis–trans isomers (of both the alkene and the
cycloalkane types) are diastereomers. Molecules that contain more than one
chiral center can also exist in diastereomeric as well as enantiomeric forms.
DESIGNATING HANDEDNESS (D,L)
USING FISCHER PROJECTION
FORMULAS
Enantiomers are said to be optically active because of the way they
interact with plane-polarized light. An optically active compound is a
compound that rotates the plane of polarized light. A dextrorotatory compound
is a chiral compound that rotates the plane of polarized light in a clockwise
direction (means to the right, the Latin dextro means “right). A levorotatory
compound is a chiral compound that rotates the plane of polarized light in a
counterclockwise (to the left, the Latin Levo means “left”) direction.
A Fischer projection formula is a two-dimensional structural notation
for showing the spatial arrangement of groups about chiral centers in
molecules.
The D,L system used to designate the handedness of enantiomers is
extended to monosaccharides with more than one chiral center in the following
manner. The carbon chain is numbered starting at the carbonyl group end of
the molecule, and the highest-numbered chiral center is used to determine D or
L configuration. Particularly, the –OH group of the highest chiral carbon
determines the configuration. If the –OH is in the right, then it’s a D-isomer
and if the –OH is in the left, and then it’s an L-isomer.

In the present example, compounds A and B (the first enantiomeric pair)

are D-erythrose and L- erythrose; compounds C and D (the second
enantiomeric pair) are D-threose and L-threose. However, A and C has a
different relationship since they are epimers. Epimers are diastereomers whose
molecules differ only in the configuration at one chiral center. Other
diastereomeric pairs in the present example are A and D, B and C, and B and
D.
STRUCTURES AND CLASSIFICATION
OF MONOSACCHARIDE
Although there is no limit to the number of carbon atoms that can be
present in a monosaccharide, only monosaccharides with three to seven carbon
atoms are commonly found in nature. A three-carbon monosaccharide is called
a triose, and those that contain four, five, and six carbon atoms are called
tetroses, pentoses, and hexoses, respectively.
Monosaccharides are classified as aldoses or ketoses on the basis of type
of carbonyl group present. An aldose is a monosaccharide that contains an
aldehyde functional group. Aldoses are polyhydroxy aldehydes. A ketose is a
monosaccharide that contains a ketone functional group. Ketoses are
polyhydroxy ketones.

Monosaccharides are often classified by both their number of carbon

atoms and their functional group. A six-carbon monosaccharide with an
aldehyde functional group is an aldohexose; a five-carbon monosaccharide
with a ketone functional group is a ketopentose. Monosaccharides are also
often called sugars. Hexoses are six-carbon sugars, pentoses five-carbon
sugars, and so on. The word sugar is associated with “sweetness,” and most
(but not all) monosaccharides have a sweet taste. The designation sugar is also
applied to disaccharides, many of which also have a sweet taste. Thus sugar is
a general designation for either a monosaccharide or a disaccharide.
Saccharide from the latin Saccharum means sugar.
ALDOSES (D-configuration)

FAMILIAR???
I know it’s quite challenging. But was it exciting that finally you’ve got
to learn that this hand exercise has meaning? Yes, they’re structures of sugars.
First, I told you to imagine having an additional 6th finger. It is because 6
mean the total number of carbon (Hexoses). Second, numbering your fingers
but consider your index as number 1 and not the thumb, because it is in your
index finger that the first chiral carbon is present. Lastly, familiarize in your
head the counting and the position of the exercise. Zero for the first sugar,
Allose, it is because it doesn’t have any chiral center. Now, you’ve tried doing
it but only with your right hand or the right or D-configuration. However, then
again because of its handedness, sugars also have left or L-configuration.
Hence, practice this exercise both with your right and left hands and now you
can name them. Let’s see about how ketoses would look like.
This table shows the possible number of optical isomer that the sugar (aldoses
or ketoses) structures can be made based on the number of chiral
centers/carbons and the location of the hydroxyl (-OH) group in the each of the
chiral centers/carbons. The higher the number of chiral center/carbon, the
higher is the possible number of optical isomer.

The 16 optical isomer of aldohexoses

KETOSES (D-configuration)

Do you agree that they somehow look the same as aldohexoses? Yes!
Although there major difference is that the second carbon is not a chiral center.
Hence, these ketohexose structures that somehow look the same as other
alhohexoses are epimers at carbon 2.
EXAMPLE OF EPIMER:
IMPORTANT SACCHARIDE
CYCLIC MONOSACCHARIDE:
HAWORTH PROJECTION FORMULA
Fischer projection formulas are useful for describing the stereochemistry
of sugars, but their long bonds and right-angle bends do not give a realistic
picture of the bonding situation in the cyclic forms, nor do they accurately
represent the overall shape of the molecules. Haworth projection formulas are
more useful for those purposes. A Haworth projection formula is a two-
dimensional structural notation that specifies the three-dimensional structure
of a cyclic form of a monosaccharide. The cyclic forms of monosaccharides
result from the ability of their carbonyl group to react intramolecularly with a
hydroxyl group. Structurally, the resulting cyclic compounds are cyclic
hemiacetals or hemiketals.
A cyclic monosaccharide containing a six-atom ring is called a pyranose
(only aldohexose is capable), and one containing a five-atom ring is called
furanose (aldopentose and ketohexose are capable of forming) because their
ring structures resemble the ring structures in the cyclic ethers pyran and furan,
respectively.

The hemiacetal carbon atom present in a cyclic monosaccharide

structure atom is called the anomeric carbon atom. An anomeric carbon atom
is the hemiacetal carbon atom present in a cyclic monosaccharide structure. It
is the carbon atom that is bonded to an -OH group and to the oxygen atom in
the heterocyclic ring. Cyclic monosaccharide formation always produces two
stereoisomers— an alpha form and a beta form. These two isomers are called
anomers. Anomers are cyclic monosaccharides that differ only in the positions
of the substituents on the anomeric (hemiacetal) carbon atom. The a-
stereoisomer has the -OH group on the opposite side of the ring from the -
CH2OH group, and the b-stereoisomer has the -OH group on the same side of
the ring as the -CH2OH group.

Note: This pyran form is only for ALDOHEXOSES (bonding C1 & C5)

CYCLIC FORMS OF OTHER MONOSACCHARIDE

FURAN KETOhexose: C2 & C5 FURAN ALDOpentose:

C1 & C4
Haworth projection
Example:
REACTIONS OF MONOSACCHARIDE
Five important reactions of monosaccharides are oxidation to acidic
sugars, reduction to sugar alcohols, glycoside formation, phosphate ester
formation, and amino sugar formation. Remember, however, that other
aldoses, as well as ketoses, undergo similar reactions.

Oxidation to Produce Acidic Sugars

The redox chemistry of
monosaccharides is
closely linked to that of
the alcohol and aldehyde
functional groups.

ACIDIC SUGARS
Reduction to Produce Sugar Alcohols
The carbonyl group present in a monosaccharide (either an aldose or a
ketose) can be reduced to a hydroxyl group, using hydrogen as the reducing
agent. For aldoses and ketoses, the product of the reduction is the
corresponding polyhydroxy alcohol, which is sometimes called a sugar
alcohol. For example, the reduction of D-glucose gives D-glucitol.
D-Glucitol aka D-sorbitol have
properties similar to those of the trihydroxy
alcohol glycerol. These alcohols are used as
moisturizing agents in foods and cosmetics
because of their affinity for water. D-Sorbitol
is also used as a sweetening agent in chewing
gum; bacteria that cause tooth decay cannot
use polyalcohols as food sources, as they can glucose and many other
monosaccharides.

Glycoside formation
Hemiacetals were shown to
react with alcohols in acid
solution to produce acetals.
Because the cyclic forms of
monosaccharides are hemiacetals,
they react with alcohols to form
acetals, like the reaction of b-D-glucose with methyl alcohol.
The general name for monosaccharide acetals is glycoside. A glycoside
is an acetal formed from a cyclic monosaccharide by replacement of the
hemiacetal carbon -OH group with an -OR group. It can exist both in alpha
and beta form.

Phosphate Ester Formation

The hydroxyl groups of a
monosaccharide can react with inorganic
oxyacids to form inorganic esters.
Phosphate esters, formed from phosphoric acid and various monosaccharides.
For example, specific enzymes in the human body catalyze the esterification of
the hemiacetal group (carbon 1) and the primary alcohol group (carbon 6) in
glucose to produce the compounds glucose 1-phosphate and glucose 6-
phosphate, respectively.
These phosphate esters of glucose are stable in aqueous solution and
play important roles in the metabolism of carbohydrates.

Amino Sugar Formation

If one of the hydroxyl groups of a monosaccharide is replaced with an
amino group, an amino sugar is produced. In naturally occurring amino sugars,
of which there are three common ones, the amino group replaces the carbon 2
hydroxyl group. The three common natural amino sugars are.

Amino sugars and their N-acetyl derivatives are important building

blocks of polysaccharides found in chitin and hyaluronic acid. The N-acetyl
derivatives of D-glucosamine and D-galactosamine are present in the
biochemical markers on red blood cells, which distinguish the various blood
types
Disaccharides
A monosaccharide that has cyclic forms (hemiacetal forms) can react with an
alcohol to form a glycoside (acetal). This same type of reaction can be used to
produce a disaccharide, a carbohydrate in which two monosaccharides are
bonded together. In disaccharide formation, one of the monosaccharide
reactants functions as a hemiacetal, and the other functions as an alcohol.

The bond that links the two

monosaccharides of a
disaccharide (glycoside)
together is called a glycosidic
linkage. A glycosidic linkage
is the bond in a disaccharide
resulting from the reaction
between the hemiacetal carbon
atom -OH group of one monosaccharide and an -OH group on the other
monosaccharide. It is always a carbon–oxygen– carbon bond in a disaccharide.
It was noted that a cyclic monosaccharide contains a hemiacetal (anomeric)
carbon atom. Many disaccharides contain both a hemiacetal carbon atom and
an acetal carbon atom, as is the case for the preceding disaccharide structure.
Hemiacetal and acetal locations within disaccharides play an important role in
the chemistry of these substances.

Tabulation of Disaccharide
OLIGOSACCHARIDES
These are saccharides that contain three to ten monosaccharide units
bonded to each other via glycosidic linkages. Two naturally occurring
oligosaccharides found in onions, cabbage, broccoli, brussel sprouts, whole
wheat, and all types of beans are the trisaccharide raffinose and the
tetrasaccharide stachyose.
TRISACCHARIDE: TETRASACCHARIDE:

RAFFINOSE composed of: STACHYOSE composed of:

 -D-galactose  -D-galactose
 -D-glucose  -D-galactose
 -D-fructose
 -D-glucose
 -D-fructose

IMPORTANCE OF OLIGOSACCHARIDES
The type of blood a person has (O, A, B, or AB) is determined by the
type of oligosaccharide that is attached to the person’s red blood cells.
Four monosaccharides contribute to the make-up of the oligosaccharide
“marking system.”
Polysaccharides
A polysaccharide is a polymer that contains many monosaccharide units
bonded to each other by glycosidic linkages. Polysaccharides are often also
called glycans. Glycan is an alternate name for a polysaccharide. Unlike
monosaccharides and most disaccharides, polysaccharides are not sweet. They
have limited water solubility because of their size. However, the -OH groups
present can individually become hydrated by water molecules. The result is
usually a thick colloidal suspension of the polysaccharide in water.
Polysaccharides, such as flour and cornstarch, are often used as thickening
agents in sauces, desserts, and gravy.
Parameters to distinguish polysaccharides:
1. The identity of the monosaccharide repeating unit(s) in the polymer chain.
a. Homopolysaccharide/glycan - only one type of monosaccharide monomer
b. Heteropolysaccharide/glycan - with more than one (usually two) type of
monosaccharide monomer
2. The length of the polymer chain.
3. The type of glycosidic linkage between monomer units.
4. The degree of branching of the polymer chain.

Types of polysaccharides
A. STORAGE POLYSACCHARIDE: used as an energy source in cells.
Examples are starch and glycogen.
B. STRUCTURAL POLYSACCHARIDE: serves as a structural element in
plant cell walls and animal exoskeletons like chitin and cellulose.

C. ACIDIC POLYSACCHARIDE with a disaccharide repeating unit in which

one of the disaccharide components is an amino sugar and one or both
disaccharide components has a negative charge due to a sulfate group or a
carboxyl group. Acidic polysaccharides are heteropolysaccharides.
Ex. hyaluronic acid & heparin
SPECIAL GROUP:
GLYCOSAMINOGLYCANS (GACS)
-aka mucopolysaccharides, or negatively charged polysaccharides.
These are large linear polymers of repeating disaccharide units, commonly
containing one or another amino sugar as one of the monomers in the
disaccharide units.
GENERAL ROLE:
 Mechanical support
 Cushioning of joints
 Cellular signals in cell proliferation and cell migration
 Inhibitors of certain enzymes
LOCATION:
 Found outside cells
 Cell surface
 Part of extracellular matrix
 Or attached to protein core to
form proteoglycans.

PROTEOGLYCANS:
 When glycosamnoglycans are
attached to a protein molecule the
compound is called proteoglycan
(proteoglycans =
Glycosaminoglycans + proteins).
 Are more carbohydrate than
protein, hence their properties are
mainly determined by the
carbohydrate portion of the
molecule.
 The carbohydrate moieties may contain carboxylic acids or sulfated sugars
thus the GAG chain carry negative charge.

PROTEOGLYCAN STRUCTURE: Core protein strands are heavily

modified keratin sulfate and chondroitin sulfate. The core protein strands are
held in a complex with s strand of hyaluronic acid by link proteins.
EXAMPLES OF GLYCOSAMINOGLYCANS (GAGS)
 chondroitin sulfate
 heparin sulfate
 keratan sulfate
 dermatan sulfate

HEPARAN SULFATE (HS)

 Sulfated polysaccharide found as a component of cell-surface proteoglycans
as a component of cell-surface proteoglycans in mast cells and in the surface
of endothelial cells lining blood vessels
 Composed of repeating units of N-acetylglucosamine and uronic acids.
 Sulfate ester formation can be found at several positions on these residues
and the acetyl group on N-acetylglucosamine may be replaced by sulfate group
(see heparin structure)
FUNCTION: After an injury to tissue, the olisaccharides derived from this
GAG are released to:
 Help mediate the inflammatory response
 Promote activity by growth factors, chemokines and cytokines
 Recruit leukocytes to the injury site
 As anticoagulant in the form of pentasaccharide sequence, HEPARIN.
Note: Heparin is much smaller than heparin sulfate and that is not linked to a
protein core. It is also more sulfated than the average random polysaccharide
sequence in heparin sulfate.

CHONDOITIN SULFATE (CS):

 Contains alternating residues of glucuronic acid and galactose N-acetyl 4-
sulfonate
 Structural polysaccharide of ligaments, cartilage and tendons
 ROLE: to lend mechanical support and flexibility to tissue to help form skin
and cartilage

DERMATAN SULFATE (DS):

 Closely related GAG, which is composed of glucuronic acid and N-
acetylgalactosamine
 Structural polysaccharide in skin

KERATAN SULFATE (KS):

 Formed form alternating units of galactose and sulfated N-acetylgucosamine
 Found primarily in the cornea of the eye and in joint cartilage for mechanical
support and structural role
 Structural polysaccharide in nails

OTHER NATURAL POLYSACCHARIDE OF INTEREST

AGAR
 Linear polymer of sulfated and unsulfated galactose prepared form marine
algae – agarose
 W/ alternating copolymer of galactose and 3,6-anhydrous-galactose
 Not a proteoglycan but is purely carbohydrate
 When dissolves in hot water and then cooled, it forms gels
 Also used as food additive to chicken liquid suspensions
INULIN
 Is a polysaccharide of fructose (and hence a fructosan found in tubers and
roots of dahlias, artichokes, and dandelions.
 It is readily soluble in water and is used to determine the glomerular
filtration rate.
DEXTRINS
 Are intermediates in the hydrolysis of starch.
Mucopolysaccharidoses (MPS) - are a group of metabolic disorders caused by
the absence or malfunctioning of lysosomal enzymes needed to break down
molecules called glycosaminoglycans (GAGs).

Degradation of the glycosamino glycan hepararan sulfate by lysosomal

enzymes, indicating sites of enzyme deficiencies in some representative
mucopolysaccharidoses (MPS). GlcUA and IdUA= glucuronic and iduronic
acids; GalNAc=N-acetylgalactosamine; GlcNAc=N-acetylglucosamine;
GlcN=glucosamine; S=sulfate (Lippincott 2017)

CARBOHYDRATES (PPT)
Introduction: and nitrogen. That is why, instead of
carbon, hydrogen, and oxygen, or
 Hydrates of carbon substances containing carbon,
 Any of a large group of organic hydrogen, and oxygen, they chose to
compounds occurring in foods redefine carbohydrates as a
and living tissues and including polyhydroxyaldehyde, a
sugars, starch, and cellulose. polyhydroxyketone, or a compound
that yields polyhydroxyaldehydes or
 Contain hydrogen and oxygen
polyhydroxyketones upon hydrolysis.
in the same ratio as water (2:1)
with the general formula
Cn(H2O)n or CnH2On.
 It is a polyhydorxy aldehyde MoNOSACCHARIDES
(aldose), a polyhydoxy ketone
(ketose), or a compound that
:
yields polyhydorxy aldehydes  Carbohydrate that contains a
or polyhydoxy ketones upon single polyhydroxy aldehyde or
hydrolysis. polyhydroxy ketone unit.
 Contains one sugar unit.
 Examples: Glucose, Fructose,
Why did they change Galactose.
the meaning of the OLIGOSACCHARIDE
carbohydrates? S:
They discovered that not
 Carbohydrate that contains two
all carbohydrates contain only carbon,
to ten monosaccharide units
hydrogen, and oxygen upon close
covalently bonded to each
study. Some of our carbohydrate
other.
derivatives are widely distributed, and
 Particularly divided into Nine
they have only recently discovered
depending on how many sugar
this one. Other elements found
units will be yield.
in carbohydrates also include sulfur
  Disaccharides, tetrasaccharides, OLIGOSACCHARIDES
etc.
 Disaccharides – sugars that will
yield units. MONOSACCHARIDES
 Examples: Maltose (2 glucose
units), Sucrose (glucose & ALDOSE
fructose), Lactose (glucose &
 Sugars that contains the
galactose)
aldehyde functional group.
 Monosaccharide that contains
POLYSACCHARIDES: an aldehyde functional group.
 Polymeric carbohydrate that Aldoses are polyhydroxy
contains as many aldehydes.
monosaccharide units
covalently bonded to each Ketose
other.
 Monosaccharide that contains a
 Examples: Starch, Glycogen,
ketone functional group as a
Cellulose
final product.
 Starch – vastly distributed in
 Example: Fructose & Ribose
plants which functions as
storage form of plants.
 Common sources of starch:
Rice (oryza sativa), Potato Functions of
(solanum tuberosum), Cassava
(manihot esculenta), Wheat. carbohydrates
 Glycogen – generally found in  Provide energy through
animals. oxidation.
 Cellulose – substances that are  Storage, in the form of
responsible for the cell wall of glycogen, provides a short-term
plants. energy reserve.
 Supply carbon atoms for the
synthesis of other biochemical
Carbohydrates: substances (proteins, lipids, and
nucleic acids).
hydrolysis  Form part of the structural
POLYSACCHARIDES framework of DNA and RNA
molecules.
  Linked to lipids are structural o Building blocks of
components of cell membranes. proteins L-phenylalanine
 Linked to proteins that function  The chirality of our sugars its
in a variety of cell-cell and cell- capacity to rotate to the left will
molecule recognition. rotate to the right is a limiting
step in terms of the
functionality and so as effects
CHIRALITY 
of our sugar.
The system in our body will be
IMPORTANCE: 
utilizing the dextro form.
Dextro form is can be utilized
 In human body chemistry, right- more by Asians such as
handed and left-handed forms Filipinos.
of a molecule often elicit  Bacteria’s inclination will be
different responses within the more of the Levo form.
body.  We utilize the form of our
 Sometimes both forms are sugar, while we utilize further l-
biologically active, each form form of our protein.
giving a different response;  Bacteria utilizes l-form of the
sometimes both elicit the same group of sugars, while they also
response, but one form’s utilize the d-form of the
response is many times greater proteins.
than that of the other; and
sometimes only one of the two
forms is biochemically active Superimposable mirror
.
o D-epinephrine (dextro image
epinephrine) is 20x
 These are mirror images that
greater than its response
coincide at all points when the
to L-epinephrine
images are laid upon each other.
o Dextro-epinephrine – is a
form of epinephrine that Nonsuperimposable
rotates to the right.
o Building blocks of mirror image
monosaccharide are
right-handed (D-glucose)
  These are mirror images where o Stereoisomers whose molecules
not all points coincide when the are not mirror images of each
images are laid upon each other. other.

Chiral center Fischer projection

 An atom in a molecule that has
four different groups
formula
tetrahedrally. o A two dimensional structural
notation for showing the spatial
Chiral molecule arrangement of groups about
 Molecule whose mirror images chiral centers in molecules.
are not superimposable.

Achiral molecule Haworth projection

 Molecule whose mirror images formula
is superimposable.
o Walter Norman Haworth (1883-
1950)

Stereoisomerism
 Isomers that have the same
molecular and structural More structural molecular formula on
formulas but differ in the the 1st uploaded video…Watch it
orientation of atoms in space. again and again!

Enantiomers
 “enantios” – opposite
 Stereoisomers whose molecules
are nonsuperimposable
 Left & right-handed

Diasteromers
CLASSIFICATION OF carbohydrates
There are three ways of classifying carbohydrates. Firstly, it is based on the
number of carbon atoms. Second, is based on the molecular size or the number
of sugar units. Lastly, will be based on the functional group present on their
structure. However, we group our carbohydrates based on the molecular size
or based on the number of sugar units that is being observed way before.
Terms such as monosaccharide, disaccharides, oligosaccharides, and
polysaccharides exist.

BASE ON trioses are important

intermediates in the process of
MOLECULAR SIZE glycolysis, a series of reactions
whereby glucose is converted
MONOSACCHARIDE into two molecules of pyruvate.
D-Glyceraldehyde is a chiral
 It is a carbohydrate that molecule, but dihydroxyacetone
contains a single polyhydroxy is not.
aldehyde or polyhyroxy ketone
unit.
 It cannot be broken down into More on the video (2nd)…
simpler units by hydrolysis
reactions. Disaccharide
 Naturally occurring
 Carbohydrate that contains two
monosaccharide have from
monosaccharide units.
three to seven carbon atoms;
 Covalently bonded to each
five- and six-carbon species are
other
especially common.
 Crystalline, water-soluble
 Pure monosaccharide are water-
substances.
soluble, white, crystalline
 Example: Sucrose (table sugar)
solids.
and lactose (milk sugar).
3C D-Glyceraldehyde &  Hydrolysis of a disaccharide
Dihydroxyacetone produces two monosaccharide
units.
o The simplest of the
monosaccharide, these two
Two monosaccharide are bonded carbon#4. Therefore, the
together by a glycosidic bond through glycosidic linkage that bonds
a dehydration synthesis. Which means the two sugars together is found
that we should be taking one hydrogen in carbon #1 and so as carbon
from one sugar and hydroxide #4.
functional group or one hydroxyl o Maltose is a reducing sugar.
found in the other sugar, so that makes o Hydrolysis of maltose is done
the H2O and then its linkage with by the enzyme maltase, wherein
what we call the glycosidic acid. it yields upon hydrolysis, upon
 Glycosidic linkage – is the bond breaking them down it will
in a disaccharide resulting from yield two glucose units
the reaction between the o Α-Maltose, β-Maltose, and
hemiacetal carbon atom -OH open-chain aldehyde form are
group of one monosaccharide the 3 forms of maltose in
and -OH group on the other aqueous solution.
monosaccharide. Cellobiose (2 D-glucose)
Maltose (2 D-glucose) o Like maltose, celliobiose
o Malt sugar, one-third as sweet contains two D-glucose
as sucrose, is produced monosaccharide units. It differs
wheneverthe polysaccharide from maltose in that one of the
starch breaks down, as happens D-glucose units – the one
in plants when seeds germinate functions as hemiacetal – must
and in human beings during have α or β configuration
starch digestion. It is common instead of the α-configuration
ingredient in baby foods and is for maltose. This change in
found in malted milk. Malt configuration results in β (1 : 4)
(germinated barley that has glycosidic linkage. Meaning,
been baked and ground) maltose and cellobiose are
contains maltose – an made up of two glucose units.
interesting compound because However, they differ in the
of its use in alcohol production glycosidic linkage in which
(fermention). maltose has α(1 : 4) glycosidic
o Maltose is bonded by α(1 : 4) link whereas cellobiose has β (1
glycosidic link which means : 4) glycosidic link.
they are bonded together with o Like maltose, cellobiose is a
the carbon #1 and so is reducing sugar, has three
 isomeric forms in aqueous
solution, and upon hydrolysis
produces 2 D-glucose
molecules, wherein the enzyme
that is responsible for the
hydrolysis is the cellobiose.
o Unique characteristics of our
enzymes is that it is specific. It
will only undergo a chemical
reaction will under a specific
substance. Example, maltose
will only hydrolyze or undergo
reaction with maltase, whereas
cellobiose will undergo
chemical reactions for
cellobiose.
Lactose (D-Galactose & D-
Glucose)
Commonly known as Milk Sugar.
Major sugar found in milk.
Uses:
- Ingredient in infant formulas that are
designed to simulate mother’s milk.
- LACTOSE AS AN EXCIPIENT
used as a filter or filler-binder.
- cost effectiveness;
- availability;
- bland taste;
- low hygroscopicity;
- compatibility with active
ingredients and
other excipients;
- excellent physical/chemical
stability;
- water solubility

Β-D-galactose unit + α-D-

glucose unit joined by a β (1
Conditions Associated with  Cataracts
Lactose  Jaundice
 Enlarged liver
1.) Lactase persistence – used to
 Kidney damage
describe the condition where milk-
drinking ability continues into
adulthood.
2.) Lactose intolerance – a condition
in which people lack the enzyme
Sucrose (D- Fructose & D-
lactase, which is needed to hydrolyze Glucose)
lactose to galactose and glucose. This is composed of α-D-glucose and
Why is it dangerous? β-D-fructose, commonly known as
Because lactose inside our body or the Table sugar. It is the most abundant of
lactose molecules remain invented in all disaccharides and occurs
undigested, they attract water to throughout the plant kingdom.
themselves causing fullness,
We have a lot of sources of sucrose.
discomfort, and causing cramping,
However, there are three main sources
nausea and diarrhea.
of sucrose/table sugar which are sugar
CAUSES: cane, sugar maple, and sugar beets.
- Genetic defect The glycosidic linkage is not α(1 : 4)
- Physiological decline with age linkage, as was the case for maltose,
- Injury to the mucosal lining of the cellobiose and lactose. It is instead an
intestines alpha, β(1 : 2) glycosidic linkage.
3.) Galactosemia – caused by the  Sucrase, the enzyme needed to
absence of one or more of the break the alpha, beta(1 : 2)
enzymes needed for the conversion of linkage in sucrose, is present in
galactose to glucose. the human body. Sucrose
In people with this condition, hydrolysis (digestion) produces
galactose and its toxic metabolic an equimolar mixture of
derivative galactitol (dulcitol) glucose and fructose called
accumulate in the blood. invert sugar.
- can cause mental retardation in When sucrose is cooked with
infants and even death. acid-containing foods such as
Galactosemia can cause the following: fruits or berries, partial
hydrolysis takes place, forming
 Brain damage some invert sugar. Jams and
 jellies prepared in this manner
are actually sweeter than the
pure sucrose added to the
original mixture because one-
to-one mixtures of glucose and
fructose taste sweeter than
sucrose.

H+ or sucrose
D-sucrose + H2O--------D-glucose + D-fructose

Invert sugar
Changing Sugar Patterns: Oligosaccharide
Decreased Sucrose
These are carbohydrates that contain 3
1.) HFCS / High-fructose corn syrup to 10 monosaccharide units bonded to
- Sweetener for food and beverages. each other via glycoside linkages.
A. HFCS42 Two naturally occurring
B. HFCS90 oligosaccharide in onions, cabbage,
C. HFCS55 broccoli, brussel sprouts, whole
2.) Sugar substitutes of sucrose wheat, and all types of beans:
- saccharin a) Raffinose – trisaccharide,
- sodium cyclamate galactose, and fructose.
- aspartame (nutra sweet) b) Stachyose – tetrasaccharide,
3.) Derivatives of sucrose galactose, glucose, and fructose
with additional galactose.
a. Sucralose – is synthesized from Humans lack the digestive
sucrose by substitution of three enzymes necessary to
chlorine atoms for hydroxyl metabolize either raffinose or
groups. stachyose. Hence these
- heatstable oligosaccharides, when ingested
- 600x sweeter than in food, pass undigested into the
sucrose large intestine causing
- calorie free discomfort.
b. Neotame – an aspartame c) Solanine – a toxin found in the
derivative. potato plant, is another example
- 7000x sweeter than of an oligosaccharide-
sucrose containing “complex’ molecule.
The same two amino acids are present - Alkaloid and
as in aspartame. It differs structurally trisaccharides of
from aspartame in that a 3,3- b-l-rhamnose,
dimethylbuthyl group is attached to b-d-glucose
the terminal –NH2 group of b-d-galactose
aspartame. This “bulky” attachment
prevents the breakdown of neotame
into its component amino acids, as
Blood types and
occurs for aspartame. Hence, oligosaccharides
individuals with PKU can use
neotame without concern. BIOCHEMICAL MARKERS
- Oligosaccharide molecules that are 2) They have limited water
attached to the plasma membrane of solubility because of their size.
red blood cells. However, the –OH groups
present can individually become
The absence or presence of a fifth
hydrated by water molecules.
monosaccharide (attached to the
The result is usually a thick
second galactose) determines blood
colloidal suspension of the
type. Type O blood lacks fifth
polysaccharide in water.
monosaccharide unit which contains
3) Polysaccharides, such as flour
galactose, fucose, and
and cornstarch, are often used
acetylglucosamine. Type A blood has
as thickening agents in sauces,
N-acetylgalactosamine as a fifth unit
desserts, and gravy.
which contains galactose, fucose,
acetylglucosamine and
Important
acetylgalactsamine. Type B blood has
parameters
galactose as a fifth unit that contains
galactose, fructose, that distinguish various
and N-
acetylglucosamine. Type AB blood
polysaccharides
contains blood type A and type B (or
markers. glycans) from each
General characteristics other are:
of polysaccharide 1.) The identity of the
monosaccharide repeating unit(s)
POLYSACCHARIDE – is a polymer
that contains many monosaccharide in the polymer chain.
bonded each other by glycosidic a. Homopolysaccharide is a
linkages. polysaccharide in which
 Glycan – an alternate name for only one type of
polysaccharide monosaccharide
 Are called complex monomer is present.
carbohydrates, simple
carbohydrates for mono & Examples: starch, glucan,
disaccharides. glycogen, cellulose, and
chitin.
Characteristics:
1) Polysaccharides are not sweet b) Heteropolysaccharide is a
and do not test positive in polysaccharide in which more
Tollens and Benedict’s than one (usually two) type of
solutions. monosaccharide monomer is
present
 - Aka amylum
Examples: hyaluronic acid and
heparin.
AMYLOSE
2.) The length of the polymer - Straight-chain glucose polymer,
chain. usually accounts for 15%-20% of the
starch.
3.) The type of glycosidic linkage
between monomer units. - Glucose units are connected by α(1 :
4) glycosidic linkages.
4.) The degree of branching of
AMYLOPECTIN
the polymer chain.
- A branched glucose polymer,
Division of accounts for the remaining 80%-85%
of the starch.
polysaccharide
- More water soluble because of
according to increase in branching.
importance: - Both α(1 : 4) and (1 :6)
1.) Storage polysaccharides (starch &
glycogen)
 Glycogen – is a branched
2.) Structural polysaccharides polysaccharide containing only
(cellulose & chitin) glucose unit.
3.) Acidic polysaccharides (hyaluronic - It is the glucose storage
& heparin) polysaccharide in humans and animals
and sometimes referred to as animal
starch.
STORAGE
- Liver cells and muscle cells are the
POLYSACCHARIDES storage sites for glycogen in humans.
- It is a polysaccharides that is a
storage form for monosaccharide and
is used as an energy source in cells. The glucose polymers amylose,
amylopectin, and glycogen compare
 Starch – a homopolysaccharide as follows in molecular size and
containing only glucose degree of branching.
monosaccharide units.
 Amylose: Up to 1000 glucose
- It is the energy-storage units; no branching.
polysaccharide in plants.
  Amylopectin: Up to 100,000 them as well. We never had the
glucose units. chance to break them down into a
 Glycogen: Up to 1,000,000 more simple substance
glucose units;  Chitin – the 2nd most abundant
- Highly branch points every 8- naturally occurring
12 glucose units. polysaccharide, next to
These 2 opposing processes are called cellulose. Its function is to give
glycogenesis and glycogenolysis, the rigidity to the exoskeletons of
formation and decomposition of crabs, lobsters, shrimp, insects,
glycogen, respectively. and other anthropods. It also
has been found in the cell walls
STRUCTURAL of fungi.
POLYSACCHARIDES
- contains galacturonic acid which is
- It is polysaccharide that serves as a not found in cellulose
structural element in plant cell walls
and animal exoskeletons.
 Cellulose – Gossypium ACIDIC POLYSACCHARIDES
hirsatum - Polysaccharide with a disaccharide
- The structural component of plant repeating unit in which one of the
cell walls disaccharide components is an amino
sugar and one or both disaccharide
- The most abundant naturally components has a negative charge due
occurring polysaccharide. to a sulfate group or carboxyl group.
- The “woody” portions of plants- - are heteropolysaccharides; two
stems, stalks, and trunks-have different monosaccharide are present
particularly high concentrations of this in an alternating pattern.
fibrous, water-insoluble substance
 Hyaluronic Acid – contains
- Contains amylose (a-1:4), cellulose alternating residues of N-acetyl-
(b-1:4) is an unbranched glucose B-D-glucosamine (NAG) and
polymer. D-glucuronate.
NOTE: For us humans, we don’t have USES:
the enzyme that can hydrolyze - Highly viscous hyaluronic acid
cellulose which is called cellulase. solutions serve as lubricants in the
Thus, it is impossible for us or we fluid of joints;
should not hit a trunk or stem. - Are also associated with the jelly-
However, since there are edible stems like consistency of the vitreous humor
that’s why if we eat them, we defecate of the eye. (The Greek word “hyalos”
means “glass”; hyaluronic acid
solutions have a glass-like
appearance.)
 Heparin – small highly-sulfated
polysaccharide with only 15-90
disaccharide residues per chain.
USES:
- Blood anticoagulant. It is naturally
present in most cells and released at
the site of tissue injury.
- It prevents the formation of clots in
the blood and retards the growth of
existing clots within the blood. It does
not, however, break down clots that
have already formed.
- The source for pharmaceutical
heparin is intestinal or lung tissue of
slaughter-house animals (pigs and
cows).

More on the 2nd Carbohydrate video…