BIOCHEM

5TH SEPTEMBER 2023 Phosphori Phospho

PART 1 INTRODUCTION TO BIOCHEMISTRY: THE c Acid ric Ester
Esters Group
MOLECULAR LOGIC OF THE LIVING STATE
Chemical Foundations of Biochemistry
➢ Organic Chemistry - study of the compounds of carbon Phosphori Phospho
c Acid ric
○ the cellular apparatus of living organisms is
Anhydrid Anhydrid
made up of carbon compounds
es e Group
○ biomolecules are part of the subject matter of
organic chemistry
○ the reactions of biomolecules can be Logic of Life
described by the methods of organic Living Matter
chemistry ➢ structurally complex and highly organized biological
➢ Functional Group - an atom or group of atoms that structures serve specific purposes
show characteristic physical and chemical properties ➢ actively engaged in energy transformations
➢ replicate themselves with perfect fidelity
Functional Groups of Biochemical Importance
Inanimate Matter
Class of General Characteristi Name of Example
Compou Structure c Function ➢ mixtures of relatively simple chemical compounds
nd al Group ➢ do not use energy in a systematic way to maintain
structure or do work
Alkenes Double ➢ show no capacity to reproduce in forms identical in
Bond mass, shape and structure, generation after generation

Basic Themes
Alcohols Hydroxyl ➢ all living things make use of the same types of
Group biomolecules, and all use energy
○ all living things can be studied using methods
Ethers Ethers of physics and chemistry
Group
➢ the fundamental similarity of cells of all types makes it
interesting to speculate on the origins of life
Amines Amino
Group
○ both cells and the biomolecules of which they
are made must have arisen ultimately from
very simple molecules such as (H2O, CH4,
CO2, NH3, H2, and H2)
Thiols Sulfhydry
l Group
Biomolecules
➢ all living cells have the same kinds of monomeric
Aldehyd Carbony
es l Group subunits
➢ there are underlying patterns in the structure of
biological macromolecules
Ketones Carbony ➢ the identity of each species of an organism is preserved
l Group by its possession of characteristics sets of nucleic acids
and proteins
➢ living cells include very large molecules (proteins,
Carboxyli Carboxyl
nucleic acids, polysaccharides, and lipids)
c Acids Group ○ amino acid → proteins
○ nucleotides → nucleic acids
○ monosaccharides → polysaccharides
Esters Ester ○ glycerol and 3 fatty acids → lipids
Group
Energy Production and Consumption
Amides Amide ➢ living organisms create and maintain their complex,
Group orderly structures at the expense of free energy from
their environment
➢ exergonic chemical or photochemical reactions are
coupled to endergonic processes through shared
chemical intermediates, channeling the free energy to
do work

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➢ in physical or chemical change, the total amount of (ribosomes, enzymes complexes, contractile systems,
energy in the universe remains constant, although the cytoskeleton) → organelles → cell
form of the energy may change
Structural Organization of Complex Biomolecules
Biological Information Transfer 1. Inorganic Precursors
➢ Genetic information is encoded in the linear sequence
of four kinds of subunits of DNA
➢ double-helical DNA molecule contains an internal
template for its own replication and repair
➢ linear sequence of amino acids in a protein leads to
the acquisition of a unique three-dimensional structure
by a self-assembly process
➢ individual macromolecules with specific affinity for ○ In photo: Carbon Dioxide
other macromolecules self-assemble into ○ 18-64 daltons
supramolecular complexes ○ Carbon dioxide, Water, Ammonia, Nitrogen,
➢ three-dimensional biological structures combine the Nitrate
properties of flexibility and stability 2. Metabolites

Composition of the Earth’s Crust, Seawater, and the Human Body

○ In photo: Pyruvate
○ 50-250 daltons
○ Pyruvate, Citrate, Succinate,
Glyceraldehyde-3-phosphate,
Fructose-1,6-bisphosphate, 3-Phosphoglyceric
acid
3. Building Blocks
➢ trace elements found in the human body serving
essential biological functions include: Mn, Fe, Co, Cu,
Zn, Mo, I, Ni, and Se

What Kinds of Molecules are Biomolecules

➢ H, O, C and N make up 99%+ of atoms in the human
body

ELEMENT PERCENTAGE %
○ in photo: alanine (amino acid)
○ 100-350 daltons
Hydrogen 63%
○ AMino acids, Nucleotides, Monosaccharides,
Fatty acids, Glycerol
Oxygen 25.5%
4. Macromolecules

Carbon 9.5%

Nitrogen 1.4%

➢ hydrogen is an important element of carbon

containing compounds
➢ water H2O is most abundant molecule in living systems
➢ carbon is a very important element in living systems
compared to non living systems ○ in photo: Protein
➢ organic compounds make up living systems ○ 10^3-10^9 daltons
○ Proteins, Nucleic acids, Polysaccharides, Lipids
Hierarchy of Increasing Molecular Complexity 5. Supramolecules
➢ Precursors from the environment (H2O, CO2, NH3, N2)
→ Metabolic intermediates → Building blocks →
Macromolecules → Supramolecular assemblies

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➢ Note: a polysaccharide chain is not an informational

chain

Directionality in Macromolecules
➢ Proteins

○10^6-10^9 daltons
○Ribosomes, Cytoskeleton, Multienzyme
complexes
6. Organelles

➢ Polysaccharides

○ Nucleus, Mitochondria, Chloroplasts,

Endoplasmic reticulum, Golgi apparatus,
Vacuole
7. Cell

➢ Nucleic acids

Properties of Biomolecules Reflect their Fitness to the Living

Conditions
➢ Macromolecules and their building blocks have a
sense of directionality
➢ Macromolecules (proteins, nucleic acids) are
informational
○ identify living systems
○ differentiates humans
➢ Biomolecules have characteristic three-dimensional
architecture
○ otherwise, (1) no effect, (2) molecule wont
function efficiently, or (3) molecule will be
useless
➢ Weak forces maintain biological structure and
determine biomolecular interactions

Informational Macromolecules
➢ strand of DNA

➢ polypeptide segment

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CHAPTER 1: CARBOHYDRATES An example would be how D-erythrose and D-threose differ only
in the placement of the OH group on carbon number 2, and yet
INTRO TO THE CONCEPT they are two completely different monosaccharides.
Concept Heading 1
Carbohydrates
➢ A polyhydroxyaldehyde or polyhydroxyketone, or a
substance that gives these compounds on hydrolysis
➢ Monosaccharides are the primary building blocks of
carbohydrates as amino acids are to proteins.
➢ They have the general formula CnH2nOn and typically
only have 3-8 carbon atoms
➢ Aldoses are monosaccharides with aldehyde groups
➢ Ketoses are monosaccharides with ketone groups
➢ Trioses are the simplest carbohydrate
monosaccharides containing 3 carbon atoms, an The following are the main examples of monosaccharide
example would be glyceraldehyde. aldoses and ketoses.

The aldoses shown below begin with 3 carbon atoms up to 6.

Glyceraldehyde is an example of an aldose triose

monosaccharide
Fischer Projections
➢ Two dimensional representations showing the
configuration of certain molecules

Mnemonic for Memorizing the Aldohexoses:

All Altruists Gladly Make Gums In Gallon Tanks

Allose - Altrose - Glucose - Mannose - Gulose - Idose - Galactose

- Talose

The ketoses shown below begin with 3 carbon atoms up to 6.

➢ Their classification depends on the number of carbon
atoms in their structure

Ketotriose Aldotriose 3 carbon

atoms

Ketotetrose Aldotetrose 4 carbon

atoms

Ketopentose Aldopentose 5 carbon

atoms

Ketohexose Aldohexose 6 carbon

atoms

There is variety in the kind of carbohydrate as the number of

carbon atoms increases due to the position of the hydroxyl
groups in each.

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Stereoisomerism

Stereoisomers
➢ Have the same molecular formula and structure but
differ in the arrangement of atoms in space

Enantiomers
➢ Stereoisomers that are non-superimposable mirror
images
➢ non-superimposable means that they cannot be
D,L Monosaccharides stacked on top of each other as they will not be the
➢ According to the conventions made by Fsicher same as the compound below it.
➢ Dependent on the positioning of the -OH on the
penultimate carbon Diastereomers
➢ Penultimate carbon is the second to the last carbon on ➢ Stereoisomers that are not mirror images
the monosaccharide ➢ they are non-superimposable
➢ Relies on the positioning of the penultimate carbon
because when a monosaccharide adds new carbons Epimers
(with a cyanide), it stacks on top of the chain, leaving
➢ 2 sugars that differ in configuration at only one chiral
the penultimate carbon untouched and constant
center are epimers
➢ D-sugars are predominate in nature (and in humans)
➢ D,L do not specify the sign of rotation of plane
Stereoisomerism Examples
polarized light

D-Monosaccharides
➢ -OH is on the right of the penultimate carbon

L-Monosaccharides
➢ -OH is on the left of the penultimate carbon

➢ These sugars are stereoisomers and diastereomers

➢ These sugars are stereoisomers and enantiomers

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Cyclic structures with an oxygen atom as a part of the ring,

could be compared to a pyran, therefore could be referred to
as pyranose or pyran-like

Cyclic Structures
➢ Aldehydes and ketones react with alcohols to form
hemiacetals and hemiketals
➢ Aldehyde + Alcohol = Hemiacetal
➢ These sugars are stereoisomers, diastereomers, epimers ➢ Ketone + Alcohol = Hemiketal

Cyclic Monosaccharide Structures

Properties of D-glucose not accounted for by open-chain
structures:
➢ Glucose fails to undergo certain reactions typical of
aldehydes
○ Ex. tests negative in Molisch’s test (no purple
ring)
➢ Glucose exists in 2 isomeric forms which undergo
mutarotation from 112 to 52°C
○ Ex. powder glucose changes when mixed in
water (like how glucose is not powderlike
inside the body)

It was said that it is important to take note of glucose as acting in

solution, as is what nature intended which is why there are
changes in the properties of open-chain structures.

Sugar forms a Cyclic Molecule

➢ Cyclization of sugars takes place due to interaction
between functional groups on distant carbons, C1 to
C5, to make a cyclic hemiacetal
○ Hydroxyl binds with carbonyl to form 5 or 6
membered rings
○ 6 membered rings are the most stable
(according to the creator - miss)
➢ Cyclization using C2 to C5 results in hemiketal
➢ Carbonyl carbon is the new chiral center and becomes
an anomeric carbon
➢ Mutarotation - the interconversion of 2 distinct
stereoisomeric modifications of a compound yielding
an equilibrium mixture with a final rotation

The principle of converting Fischer projections to Haworth

projections entails that the OH groups positioned on the right are
to be placed on a downward line so as to act as a substituent
on the same carbon number that it was attached to. The same
applies for OH groups on the left which will be presumed an
upward position.

This is called an internal hemiacetal formation in D-glucose.

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12TH SEPTEMBER 2023
CARBOHYDRATES (CONTINUATION)
GLUCOSE
➢ D-Glucose and L-Glucose are optical isomers or
enantiomers of each other and are mirror images
➢ Carbonyl group and hydroxyl group can be clearly
seen at the structures of these molecules
➢ In any reaction that indicates the presence of a
carbonyl group, glucose is expected to give a positive
result because there is a carbonyl group in it
➢ For reactions involving hydroxyl groups, glucose should
also give positive result because there are a lot of
hydroxyl groups in it
➢ To indicate the presence of a certain functional group,
qualitative tests are done (e.g. color reactions)
➢ Subjecting glucose to tests involving hydroxyl groups,
you will give positive results which is correct
Cyclic monosaccharide structures and anomeric forms
➢ Properties of D-glucose not accounted for by open –
chain structures:
○ Glucose fails to undergo certain reactions
typical of aldehydes
■ Subjecting glucose to tests involving
the presence of carbonyl group,
glucose will give positive results in
some tests (e.g. Fehling’s test) but
there are some reactions that are
typical of aldehydes but glucose did
not give positive results even if it has
a carbonyl group (e.g. Schiff’s test)
○ Glucose exists in 2 isomeric forms which
undergo mutarotation from 112 to 52.7°
■ These molecules are optically active,
they are able to rotate the plane of
polarized light clockwise or
counterclockwise
■ Normally, you would indicate optical
activity as a property of a molecule
if it is optically active by studying the
way it rotates the plane of polarized
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light using a polarimeter that is
usually indicated in the table of
constants
■ There are many molecules that are
not optically active, but for those
that are optically active, there is an
additional information indicating
optical activity usually it is a number
or degrees because it indicates the
way a molecule rotates the plane of
polarized light in a certain direction
either clockwise or counterclockwise
■ When a glucose was subjected in
polarimetric measurement to
indicate optical activity, two
readings were gotten
■ One molecule should only have one
optical rotation
■ It was found that instead of one
optical activity, there was an optical
activity that was the result of an
equilibrium system to isomers even if
only one glucose was examined
➢ Fischer projection structures of monosaccharides
whether aldoses or ketoses show exactly where atoms
are put together and where the functional groups are
positioned
What Happens if a Sugar Forms a Cyclic Molecule?
➢ Cyclization of sugars takes place due to interaction
between functional groups on distant carbons, C1 to
C5, to make a cyclic hemiacetal
➢ Cyclization using C2 to C5 results in hemiketal
formation.
➢ In both cases, the carbonyl carbon is new chiral center
and becomes an anomeric carbon
➢ Mutarotation is the interconversion of two distinct
stereoisomeric modifications of a compound yielding
an equilibrium mixture with a final rotation
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○ Because of the partial negative character of

➢ Haworth suggested that something happens to glucose
and other monosaccharides when they are placed in
solution
➢ If you get glucose in powder form and check the
structure of that molecule, you will probably see the
structure on this image, but it makes a difference when
you carry out a reaction and put the molecule in
solution
the oxygen, electrons go more to the oxygen
than hydrogen
○ When oxygen attaches itself to the carbon
■ Hydrogen detaches as an H+
■ Electrons are taken out from the
double bond in the aldehyde; partial
negative charge is assigned to the
oxygen
■ -OH is formed
■ Hemiacetal is created
○ Hemiacetal is formed from a reaction
between an aldehyde and an alcohol
○ Haworth suggested that same thing happens
within the molecule
○ e.g. In glucose, there is a carbonyl and a lot
of hydroxyl groups so there is an internal
hemiacetal formation that happens within
glucose in solution
OPEN CHAIN STRUCTURE TO CYCLIC FORM
➢ C1: —OH should be down since it is located at the right
➢ C2: right = down
➢ C3: left = up
➢ C4: right = down
➢ C5: there is no —OH, so CH2OH is attached
➢ attach the —O— between C1 and C5

➢ Aldehyde has carbon atom linked to an oxygen via

double bond with shared shared electrons but oxygen
is more electronegative than carbon
○ Therefore, electrons go to oxygen more than
they go to carbon so oxygen gets greater
share of electrons
○ Partial positive sign can be assigned to
carbon
○ Partial negative sign can be assigned to
oxygen
○ Molecules like these can react with something
containing electrons or negative charge, so
any atom having those properties can attach
itself to the carbon
➢ Difference: configuration only at the hemiacetal
➢ Alcohol has oxygen that carries lone pair of electrons
carbon (also referred to as anomeric carbon)
that can be assigned of partial negative character
○ If pointing down: alpha
○ When you react alcohol to an aldehyde, the
○ If pointing up: beta
oxygen attaches to the carbon forming a
➢ therefore, you end up with two ring structures
hemiacetal

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CREATING A 5-MEMBERED CARBON RING
➢ Mannose is a stereoisomer of Glucose
➢ D-Mannose is a stereoisomer of D-Glucose
➢ D-Glucose and D-Mannose are diastereomers
➢ D-Glucose and D-Mannose are epimers
○ the only difference is the configuration of the
—OH on C2
○ D-Mannose has the —OH on the left, while
D-Glucose is on the right
➢ D-Galactose and D-Mannose are not epimers
○ they have more than one difference
○ on C2, D-Galactose has the —OH on the right,
while D-Mannose has it on the left
○ on C4, the —OH is on the left for D-Galactose
and right for D-Mannose
➢ D-Glucose and D-Galactose are epimers
○ the only difference is configuration at C4, in
which D-Galactose has it on the left, while
D-Glucose has on the right
➢ for every one open chain structure that undergoes
cyclization, you end up with two anomers
○ one beta (—OH is up)
○ one alpha (—OH is down)
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FRUCTOSE
➢ it is still a reaction between a carbonyl and an alcohol,
but this time, it is a ketone
○ because fructose is a ketone
➢ there will be a formation of the hemiketal
○ —H attaches to =O, creating —OH
○ R—O attaches to the carbon atom
➢ if you are aiming for a 5-membered ring, that means
that you should come up with a reaction between
—OH of C5 and the carbonyl carbon
➢ the point of attack is always the carbonyl carbon
➢ in order to create a 5-membered ring, oxygen will be
one of the members of the ring, using the oxygen of C5
○ there will be 4 carbon atoms + 1 oxygen atom
to make it 5
○ but if you use C6, it will become a
6-membered ring
➢ with the oxygen on top of the ring, it should be
connected to C5 and C2
○ it is not C1 because C1 is only an attachment
(kabit) to C2
○ C1 is not involved in the reaction but it is still
there
➢ write the corresponding configurations in order to
complete the ring
○ CH2OH will be attached to C2
○ —OH of C2: down because it is on the right
○ C3: up
○ C4: down
○ C5: CH2OH will be attached
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CYCLIZATION OF SIMPLE SUGARS

➢ Simple sugars can cyclize in two ways, forming either

furanose or pyranose structure
➢ in order to create a 5-membered ring from glucose,
—OH from C4 will react to the carbonyl; therefore, the
ring will consist of:
○ C1 - C4 + O atoms
○ C5 and C6 will only be substituents

➢ in fructose, you will carry out a reaction on C5 to create

a 5-membered ring
○ oxygen had to be one of the members of the
ring
○ C1 is not included in the cyclization, but is a ➢ PYRANOSE: 6-membered ring structure
substituent ➢ FURANOSE: 5-membered ring structure
➢ you will actually be creating two anomers
○ because you created a new chiral center TURNING FRUCTOSE INTO A 6-MEMBERED RING
and a new sp3 carbon
➢ the —OH of C6 should attack the carbonyl carbon
○ therefore, you will now have an —OH on C2,
which can be on the right or left
➢ from D-Fructose, you will have two isomeric structures:
○ alpha-D-Fructofuranose
○ beta-D-Fructofuranose

➢ most 5-carbon monosaccharides end up as

5-membered rings but 6-membered ring structures are
also known

➢ fructose is sweeter than sucrose

○ we just don't use it because it is more
expensive, and sucrose can be acquired
through plants, while you can get fructose by
a process using sucrose
○ the taste of any molecule is actually
dependent on its structure
○ when fructose cyclizes, there are a lot of
5-membered rings, but there are also some
6-membered rings
○ therefore, not only furanose is there but also
pyranose

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15TH SEPTEMBER 2023 ➢ Anomers are cyclic monosaccharides differing from

each other in the configuration of C-1 or C-2 carbon.
PART 3 CARBOHYDRATES
Simple Sugars
Cyclic Structure
➢ Monosaccharides have -OH and C=O groups in the
same molecule and exist almost entirely as 5- and 6-
membered cyclic hemiacetals
➢ anomeric carbon - the new stereocenter resulting from
cyclic hemiacetal formation
➢ anomers - carbohydrates that differ in configuration
only at their anomeric carbons

➢ Simple sugars can cyclize in two ways: (1) form
furanose or (2) form pyranose.
➢ Furanose - 5-membered ring system containing 4
carbon atoms
➢ Pyranose - 6-membered ring structure consisting of 5
carbon atoms
Quick Review of Hybridization Theory
➢ sp3, sp2, sp; generally determined using the steric
number
○ steric number (SN) - number of “connections”
(includes lone pairs); double bonds count as
only one connection
Haworth Projections
➢ 5- and 6- membered hemiacetals are represented as
planar pentagons or hexagons, as the case may be,
viewed through the edge
➢ most commonly written with the anomeric carbon on
the right and the hemiacetal oxygen to the back right
➢ the designation β- means that -OH on the anomeric
carbon is cis to the terminal -CH2OH; α- means that it is
trans
➢ a 6-membered hemiacetal ring is shown by the infix
-pyran- (pyranose)
➢ a 5-membered hemiacetal ring is shown by the infix
-furan- (furanose)
➢ 5-membered rings are so close to being planar that
Haworth projections are adequate to represent
furanoses
➢ For pyranose, the six-membered ring is more accurately
represented as a strain-free chair conformation

➢ To determine a certain group’s hybridization, subtract 1

from the steric number; ex. the steric number is 3, thus
the hybridization will be sp2

Cyclization and Other Notes

➢ if OH group appears on the right in Fischer projection
form, then the group points down in cyclization
➢ if OH group appears on the left in Fischer projection
form, then the group points up in cyclization
➢ Remember that carbon is always surrounded by four
bonds
➢ alpha D ribofuranose

➢ beta D ribofuranose
Configurational Isomers
➢ Enantiomers - Stereoisomers that are mirror images of
one another; the boxed asymmetric carbon (farthest
from aldehyde) determines D/L designation

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Oxidation Reactions
➢ The carbonyl group of a monosaccharide can be
oxidized to a carboxylic acid group by a variety of
oxidizing agents
➢ aldose → aldonic acid (mild oxidizing agent) -
carbon 1 is oxidized
➢ aldose → aldaric acid (strong oxidizing agent) -
both ends of the molecule are oxidized
➢ aldose → alduronic acid (a special kind of oxidation
and acid) - only the terminal hydroxyl that’s oxidized
➢ Diastereomers - Stereoisomers that are NOT mirror
without touching the carbonyl carbon (not a one-step
images of one another
process)
➢ The difference between glucose and gluconic acid is
the COOH in carbon number 1
○ Any monosaccharide in the presence of a
mild oxidizing agent, glucose and any aldose
is converted to aldonic acid

➢ Anomers - Stereoisomers that differ in configuration at

the anomeric carbon

➢ oxidizing agent iron+2 = rust

➢ Epimers - Stereoisomers that differ in configuration at
one carbon other than the anomeric carbon

Conformational Isomers
➢ Molecules with the same stereochemical configuration,
but differing in three-dimensional conformation

Monosaccharides Can Be Converted

to Several Derivative Forms
➢ A variety of chemical and enzymatic reactions
produce derivatives of the simple sugars.
➢ Some of the most common are:
○ sugar acids
○ sugar alcohols
○ deoxy sugars
○ sugar esters
○ amino sugars
○ acetals, ketals, and glycosides

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➢ glucuronic acid (diff from galactaric/mucic acid) -

carbon #6 lang nag-ooxidize (both ends)

Sugar Alcohols

➢ alduronic acid (different from aldonic, aldonic acids)

➢ acid plus alcohol = ester

➢ Galactose is optically active, mucic acid/galactaric
acid is not. Why? Because you can cut the molecules
into two parts – one is the mirror image of the other.
○ Molecule that lost its optical activity is called
meso compound.
Deoxy Sugars
➢ Deoxy sugars are monosaccharides with one or more
hydroxyl groups replaced by hydrogens
➢ 2-deoxy-D-ribose is a constituent of DNA
➢ Rhamnose is a component of ouabain, a toxic
“cardiac glycoside”
➢ Fructose is a component of some cell walls

➢ oxygen compounds na natanggalan ng oxygen =

deoxy-; ex. if you remove from carbon #2,
2-deoxyribo…

More Monosaccharide Derivatives

➢ Sugar alcohols are formed by mild reduction of sugars
➢ Deoxy sugars: constituents of DNA, etc.
➢ Sugar esters: phosphate esters like ATP are important
➢ Amino sugars: contain an amino group in place of a
hydroxyl group
➢ Acetals, ketals, and glycosides: basis for oligo- and
polysaccharides
○ example of reducing agent: hydrogen gas
○ when an aldehyde if reduced, it becomes
alcohol, glucose becomes glucitol, mannose
to mannitol, xylose to xylitol, galactose to
galactitol

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19TH SEPTEMBER 2023

CARBOHYDRATES
Deoxy Sugars
➢ are monosaccharides with one or more hydroxyl groups
replaced by hydrogens
➢ 2-Deoxy-D-ribose is a constituent of DNA
○ if you reduced carbon no. 2 in D-Ribose it will
be converted to alkyl
○ reaction is mediated by enzymes which are
very selective in what they do

—-->>>

deoxy derivative of L-Mannose

➢ Rhamnose is a component of ouabain

○ a toxic cardiac glycoside cyclic form of L-Mannose
○ common name for specific sugar made from
L-Galactose ➢ fucose is a component of some cell walls
○ came from mannose

Esters

➢ R and R’ are general hydrocarbon groups

➢ Oxygen attacks carbonyl carbon

PHOSPHATE ESTERS

➢ Phosphoric acid reacts with alcohol

➢ Phosphorus is less electronegative than the oxygen
hence electrons are more drawn to oxygen which
gives the phosphorus a partial positive character

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➢ carboxylic acid and phosphoric acid gets the same Amino Sugars
type of reaction – removal of water molecule
○ common reaction in metabolism

Sugar Esters
➢ Phosphate esters of glucose, fructose, an other
monosaccharides are important metabolic
intermediates
➢ the ribose moiety of nucleotides such as ATP and GTP is
phosphorylated at the 5’ position

➢ Sugars with an amino group C-2

➢ found in many oligosaccharides and polysaccharides
➢ derivatives of monosaccharides because they are
results of reactions within a monosaccharides and
some other reagent:
○ oxidizing reagent forming sugar acids
➢ a-D-Fructose-1,6-bisphosphate - carbon 1 and 6 are
○ reducing agents forming sugar alcohols
both phosphorylated
○ special reducing processes to end up with a
➢ a-D-Fructose-5-bisphosphate - carbon 5 is
deoxy sugar
phosphorylated
○ phosphoric acid
➢ Carbon 1 and terminal carbon - the one that mostly
➢ any of the OH in the amino sugar can be replaced by
gets phosphorylated
amino groups

Adenosine Triphosphate
Glycosidic Bond Formation
➢ Leads to the formation of bigger molecules
➢ Glycoside
○ A carbohydrate in which the -OH of the
anomeric carbon is replaced by -OR
○ Furanosides
■ Those derived from furanoses
○ Pyranosides
■ Those derived from pyranoses
○ This is the basis for the formation of
polysaccharides/oligosaccharides
➢ Monosaccharides
○ Building blocks of
➢ the energy that you need for endergonic reactions are polysaccharides/oligosaccharides
supplied by exergonic reactions ➢ Oligosaccharides
➢ when adenosine triphosphate undergoes its own ○ A carbohydrate consisting of 2-10
hydrolysis reaction (where one or more phosphate monosaccharides
groups is removed) the reaction is accompanied by ➢ Polysaccharides
the release of a significant amount of energy ○ A carbohydrate consisting of more than 10
monosaccharides
➢ Glycosidic Bond
○ The bond from the anomeric carbon to the
-OR group
○ An oxygen bonded between 2 carbons
where at least 1 carbon is coming from a
monosaccharide
➢ phosphoric esters
○ important in the metabolism of sugars to
provide energy
○ frequently formed by transfer of a phosphate
group from ATP
➢ ATP has numerous negatively charged oxygen beside
each other hence it experiences electronic repulsion
➢ another factor that makes the molecule willing to give
up more phosphate is because of the opposing
resonances
➢ if ATP donates a phosphate to a glucose, then you’ll be
left with adenosine diphosphate and
Glucose-6-phosphate

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○ Two units of D-glucose molecules connected

by an ɑ-(1→4) glycosidic linkage
○ Formed from the hydrolysis of starch
○ Differs from cellobiose by the confirmation of
the glycosidic linkage

Disaccharides
➢ Glycosidic linkages can take various forms; the
anomeric carbon of one sugar to any of the -OH
groups of another sugar to form a/an ɑ- or β- glycosidic
➢ Cellobiose
linkage
○ Two units of D-glucose molecules connected
by an β-(1→4) glycosidic linkage
○ Disaccharide unit of cellulose
➢ Maltose and cellobiose are two chemically different
molecules.

➢ Maltose

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➢ β-D-glucopyranosyl-(1→1)-β-D-glucopyranose
➢ β-D-glucopyranosyl-(1→1)-β-D-glucopyranoside

➢ Lactose
○ Made up of D-galactose and one unit of
D-glucose joined by a β-(1→4)-glycosidic
bond
○ Galactose is a C-4 epimer of glucose
○ Found in milk

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21ST SEPTEMBER 2023 𝛃 – D – glucopyranosyl – (1 → 4) – 𝞫 – D - glucopyranoside

PART 4 CARBOHYDRATES ➢ Remember: Glycosidic bonds occur at any of the hydroxyl

Disaccharides
groups
➢ Also known as ‘double sugar’
➢ It is formed when two monosaccharides are joined by
glycosidic linkages

| Glycosidic Linkages are formed when an anomeric carbon

binds to the -OH (hydroxyl group) of another sugar to form alpha
or beta glycosidic linkages. They are also the basis for
polysaccharide or oligosaccharide formation

Maltose
➢ A sugar (disaccharide) made up of two
alpha-D-glucose units

➢ Glycosidic linkages can take various forms; the

anomeric carbon of one sugar to any of the -OH groups
of another sugar to form a/an ɑ- or 𝛃- glycosidic linkage

Maltose

The complete name of this compound which includes its ➢ Two units of D-glucose joined by an ɑ-(1-4)- glycosidic
glycosidic linkage is: bond
➢ formed from the hydrolysis of starch
ɑ – D – glucopyranosyl – (1 → 4) – ɑ – D - glucopyranoside ➢ differs from cellobiose by the conformation of the
glycosidic linkage
The configuration of whether the glycoside is alpha or beta solely
depends on the -OH group of the latter monosaccharide, which
in this case as shown in the illustration above is another glucose
unit with -OH on the downward direction meaning that it is an
alpha

Cellobiose
➢ This disaccharide is ALSO composed of two glucose
units, however instead of using alpha 1,4 glycosidic
bonds it utilizes beta 1,4 glycosidic linkages

Cellobiose
➢ Two units of D-glucose joined by a 𝛃-(1-4)-glycosidic
bond
➢ disaccharide unit of cellulose

The complete name of this compound which includes its

glycosidic linkage is:

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Lactose
➢ Made up of D-galactose and one unit of D-glucose
joined by a 𝛃-(1-4)-glycosidic bond
➢ Galactose is an epimer of glucose at C4
➢ found in milk

Hydrolysis
➢ is a chemical process in which water is returned to a
substance, accompanied by a catalyst (enzymes) in
order to make it more efficient

Sucrose
➢ Table sugar; obtained from the juice of sugar cane and
sugar beet
➢ One unit of D-glucose and one unit of D-fructose joined
by an ɑ-(1-2)- glycosidic bond

ex. Lactose is hydrolyzed back into D-galactose and D-glucose

Raffinose and Stachyose

➢ The glycosidic linkage can occur at any direction so
long as it reaches the right numbered carbon/anomeric
carbon
➢ Raffinose is a trisaccharide that contains galactose,
glucose, and fructose
➢ It has both alpha and beta glycosidic linkages,
therefore it can be hydrolyzed into D-galactose and
sucrose
➢ Stachyose is a tetrasaccharide consisting of two
α-D-galactose units, one α-D-glucose unit, and one
β-D-fructose unit
➢ It is sequentially linked as:

Gal(α1→6)Gal(α1→6)Glc(α1↔2β)Fruf

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➢ chain of 24 to 30 units of D-glucose units

➢ joined by a-(1, 4)-glycosidic bonds
➢ branches connect by a-(1,6)-glycosidic bonds

Amylose in Water
➢ adopt a helical conformation
➢ Iodine fits in between the hydrophobic middle of an
amylose helix (sa gitna ng coils)
➢ Iodine molecules appear indigo in color

Hydrolysis of Starch
➢ Amylase is responsible for catalyzing the hydrolysis of
a-(1,4)-glycosidic bonds
➢ 2 types of amylase differ in cleaving the (1,4) bonds

a-Amylase
Polysaccharides ➢ endoglycosidase or endoenzyme
➢ Nomenclature is based on composition and structure ○ randomly cleaves a-(1,4)-glycosidic bonds of
➢ Homopolysaccharide the amylose chain
○ contains only 1 kind of monosaccharide ○ cuts the chain into 2-5 units
➢ Heteropolysaccharide ○ produces glucose and maltose (dextrins)
○ contains several kinds of monosaccharides
○ usually around 3-4 β-Amylase
➢ Storage Molecules (Starch, Glycogen) ➢ exoglycosidase or exoenzyme
➢ Structural Molecules (Chitin, Cellulose) ○ systemic approach to cleaving
➢ Cell surface polysaccharides are recognition molecules ○ starts at the non-reducing ends and cleaves
the glucan chain into 2 units only
Starch ○ produces maltose
➢ Energy storage in plants
➢ Polymer of α-D-glucose units R-Enzyme
➢ usually 10-30% amylose and 70-90% amylopectin
➢ cleaves yung tira-tira ni alpha and beta amylases
➢ Sa kwentong kanin
➢ cleaves the a-(1,6)-glycosidic bonds of the branches
○ higher amylopectin, mas malagkit yung kanin
➢ further division of amylose to glucose
➢ cleaves the chain into dextrins (glucose)
Amylose
➢ continuous, unbranched
➢ chain of 4000 α-D-glucose units
➢ joined by a-(1, 4)-glycosidic bonds

Amylopectin
➢ highly branched

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Glycogen
➢ Energy storage in animals
➢ looks like the amylopectin but more branched
➢ constitutes up to 10% liver mass & 1-2% of muscle mass
➢ has a-(1,6) branches every 8-12 residues
➢ also gives a red-violet color with iodine
➢ Similar structure with the amylopectin but is more
complicated because animals require more energy
than plants
○ with more branches, faster breakdown of
glycogen to blood glucose for energy

Dextrans
➢ Energy storage in microorganisms
➢ Branches can be (1,2), (1,3), or (1,4)
➢ mesh-like structure
➢ Dextran as oral plaque provide protection from oral
bacteria
➢ separate molecules/proteins (binubutasan)
➢ Cross-linked dextrans are used as Sephadex Gels in
column chromatography
➢ Used in treating hemorrhage, shock, surgical
procedures, radiological imaging, antithrombotic
administration, and ophthalmic relief of xerophthalmia

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