LECTURE 1 / CARBOHYDRATE CHEMISTRY

OUTLINE INTRODUCTION TO MOLECULAR BIOLOGY

I. Introduction to Molecular Biology • Goes hand in hand with biochemistry
II. Biologic Functions of Carbohydrates • Biochemistry
III. Carbohydrates o Biochemical Substances
IV. Classification of Carbohydrates ▪ Bioinorganic Substances
A. Classification of Dietary Carbohydrates - Water (about 70%)
i. Simple - Inorganic Salts (about 5%)
ii. Complex ▪ Bioorganic Substances
B. Classification Based on Molecular Size - Proteins (about 15%)
C. Classification According to Functional Group - Lipids (about 8%)
D. Classification of Monosaccharides Based on Carbon - Carbohydrates (about 2%)
Atom They Contain - Nucleic Acids (about 2%)
i. Examples of Monosaccharides
V. Carbon Numbering
• Proteins & Nucleic Acids – has nitrogen
A. D and L Configuration
• Carbohydrates and Lipids – Carbon, hydrogen and
VI. Asymmetric Carbon
VII. Importance of Handedness
oxygen
VIII. Isomers • Galactose – monosaccharide
A. Constitutional Isomers • Deoxyribose for DNA
B. Stereoisomers • Ribose – for RNA
i. Enantiomers • Lactose – milk
ii. Diastereomers • Sucrose – table sugar
IX. Different Ways of Representing Sugar • Chirality – symmetrical carbon
Conformation/Projection • Starch – gives us energy (rice, bread, pasta); plant
A. Fisher Projection origin
B. Haworth Projection Formula o Cellulose – structure fiber; carbohydrate with
C. Newman Projection structural function
X. Optical Activity
• Collagen – animal origin
A. Hemiacetal Formation
i. Cyclic Formation of Monosaccharides • Photosynthesis – synthesis of carbohydrates from
B. Hemiketal Formation water, carbon, and sunlight; oxygen is released
XI. Biochemically Important Monosaccharides C6H12O6 + 6O2 ==➔ 6CO2 + 6H2O + energy
A. D-Glyceraldehyde and Dihydroxyacetone • Glycolysis – for us to derive energy from
B. D-Glucose carbohydrates; opposite reaction of photosynthesis
C. D-Galactose • Glucose metabolization - process where we eat
i. HBA1c- glycosylated hgbA1 carbohydrates, they breakdown into simple sugars
D. D-Fructose which all turn into glucose which flows through the blood
E. Deoxyribose to the cells.
F. D-Ribose
i. D-Ribose and Deoxy-D-Ribose BIOLOGIC FUNCTIONS
XII. Reactions of Monosaccharides • Storage form of energy
A. Oxidation Reactions to Produce Sugar Acid o Glycogen – animals; composed of several glucose
B. Reduction to Produce Sugar Alcohols (mainly stored in the liver); glycogen in the liver will be
C. Glycoside (Acetal) Formation catabolized to glucose
D. Amino Sugar Formation
o Starch – plants
E. Phosphate Ester Formation
• Source of energy
XIII. Lobry–De Bruyn–Van Ekenstein Transformation
XIV. Epimerization
• 1 gram of carbohydrates can yield 4 kCal
XV. Disaccharides
XVI. Oligosaccharides
• 1 cup rice = 200 calories
XVII. Polysaccharides • 3 pcs skyflakes = 150 cal
A. Biologic Function
B. Homopolysaccharide • Sources of metabolic intermediates
C. Heteropolysaccharide o Nucleic acid – DNA and RNA
o Vitamin C – humans lack the enzyme to produce vitamin
C from glucose
• Transport function
o Ceruloplasmin
o Transferrin
• Structural/Supportive functions

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 o Cellulose – main constituent of plant cell walls • aldehyde or ketone derivatives of polyhydric alcohols.
o Chitin – principal component of the exoskeleton of • Hydrated carbon
arthropods (insects and crustacea) • For every carbon, there is one water molecule
o Peptidoglycan – component of the bacterial cell wall (N- o (CH2O)n
acetylglucosamine/N-acetylmuramic acid) ▪ n = number of carbon atoms
o Proteoglycan or acid Mucopolysaccharides • Basic structure:
(glycosaminoglycans) – for our joints
▪ Antibiotic Penicillin – inhibits the synthesis of
peptidoglycan layer in the cell wall
▪ Hyaluronic acid
▪ Chondroitin sulfate – for shock absorption to
prevent direct rubbing contact of bones
▪ Keratan sulfate
▪ Dermatan sulfate
• Provides viscoelastic properties to the connective tissues
o sialoglycoproteins o Each carbon atom carries a hydroxyl group (-OH), except
o proteoglycans one, which is double bonded to an oxygen to form a
• Cell – cell recognition/cell surface receptors; attached to carbonyl group (C=O)
proteins and lipids o Deoxy – no hydroxyl; dehydrated
o Glycoproteins o Ribose – has hydroxyl group
▪ aldehyde
- if the C=O is at the terminus
- glucose – 6 carbon atoms (hexose, thus,
aldohexose)
- ribose – 5 carbon atoms (apentoses)
- deoxyribose
- galactose - aldohexose
▪ ketone
- if the C=O is internal in the chain
- Middle
- Fructose – 6 carbon atoms (ketohexose)

CLASSIFICATION OF CARBOHYDRATES
CLASSIFICATION OF DIETARY CARBOHYDRATES
SIMPLE
• monosaccharides/disaccharides
• simple sugars; easy to digest; quick sources of energy
o Sucrose – simple; can easily increase blood sugar
COMPLEX
▪ In RBC membrane, there is A-antigen and B-antigen;
these two have difference due to enzymes o Oligosaccharide – 2-10 units of monosaccharides
o Glycolipids o Polysaccharide – 10 or more units of monosaccharides
• Anticoagulant – heparin o Provide sustained energy (glycogen)
o Help regulate blood sugar irregularities (cellulose –
high-fiber diet)
“If you want to understand the function, study
o Help lower blood cholesterol
the structure”
- Francis Crick CLASSIFICATION BASED ON MOLECULAR SIZE
• These types of carbohydrates are related t each other
through hydrolysis:
CARBOHYDRATES
• aldehyde or ketone compounds with multiple hydroxyl
groups

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 CLASSIFICATION OF MONOSACCHARIDES
ACCORDING TO CARBON ATOMS THEY CONTAIN
• Three carbons (Trioses)
D-Aldoses D-Ketoses

• Monosaccharide
o Simple sugar
o Contains a single aldehyde or ketone unit with multiple
hydroxyl groups • Four carbons (Tetroses)
o Cannot be hydrolyzed into simpler compound D-Aldoses D-Ketoses
o Can be classified based on the number of carbon atoms
▪ Hexoses
- Glucose
- Fructose
- Galactose
▪ Pentoses
- Deoxyribose – 5 carbons; DNA sugar
- Ribose – 5 carbons; RNA sugar
▪ Trioses (simplest among monosaccharides)
- Glyceraldehyde – 3 carbons; aldose
- Dihydroxyacetone – 3 carbons; ketose
• Disaccharide
• Oligosaccharide • Five carbons (Pentoses)
• Polysaccharide D-Aldoses
CLASSIFICATION ACCORDING TO FUNCTIONAL
GROUP
• Polyhydroxy-aldehyde (ALDOSE)
o Aldehyde group
o C=O at terminal

D-Ketoses

• Polyhydroxy-ketone (KETOSE)
o Ketone group
o C=O at chain
• Six carbons (Hexoses)
D-Aldoses

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D-Ketoses

Primary carbinol
• Seven carbons (Heptoses) - uncommon IMPORTANCE OF THE HANDEDNESS
EXAMPLES OF MONOSACCHARIDES • Handedness – position of the OH group of the penultimate
carbon atom
• The right-handed and left-handed forms of a molecule elicit
different types of responses within the human body.
• Naturally occurring monosaccharides are almost always
“right-handed.” Common sugars are usually right handed.
D AND L CONFIGURATION
• Prefixes D and L designate the stereochemical configuration
of the asymmetric carbon farthest from the carbonyl carbon
(or the highest numbered chiral center).
o D = -OH is on the right of the Fischer formula
CARBON NUMBERING o L = -OH is on the left of the Fischer formula
• Start numbering from the end adjacent to the aldehyde or o Based on the asymmetric carbon farthest from the carbonyl
ketone group. carbon (Penultimate Carbon Atom)
ISOMERS

• compounds that have the same chemical formula but are not
identical (configuration is different)
CONSTITUTIONAL ISOMERS
• differ in the way the atoms are connected (different
functional groups and bonding pattern)
• structural
ASYMMETRIC CARBON • different functional groups/positions and bonding pattern but
• Otherwise known as “chiral” center same chemical formula
• Any carbon with four different groups attached to it STERIOISOMERS
• Chiral Center • differ in the way the atoms are arranged (same functional
groups and bonding pattern)
• spatial
• same functional groups and bonding pattern but different
position of functional group (different structural
configuration)
• isomers that have the same molecular and structural
formulas as well as bonding sequence but differ in the
orientation of atoms in space
• Formula to predict # of Isomers
• All monosaccharides have at least one asymmetric carbon o = 2 n (where n = asymmetric carbon atoms)
atom except dihydroxyacetone.

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ENANTIOMERS DIFFERENT WAYS OF REPRESENTING SUGAR
• stereoisomers whose molecules are nonsuperimposable CONFORMATION/PROJECTION
mirror images of each other FISHER PROJECTION
• Two dimensional; Straight-chain structural formula; Linear
conformation
o At the topmost will be the aldehyde; carbonyl carbon
o 5th carbon is the penultimate carbon atom
o Last carbon is the carbinol carbon

DIASTEREOMERS
• stereoisomers whose molecules have the same number of
atoms but differ in spatial configuration; non-mirror

HAWORTH PROJECTION FORMULA

• Two-dimensional structural notation that specifies the 3
dimensional structure of a ring form of a monosaccharide

o Cis-transisomers
o Conformers

• Epimers
o Differ only in one atom
o diastereomers whose molecules differ only in the
configuration at one chiral center; differ in one atom
• D or L designation is determined by the position of the
terminal CH2OH group
o D – Primary carbinol CH2OH is positioned above the ring
o L - Primary carbinol CH2OH is positioned below the ring
FISCHER FORMULA TO HAWORTH PROJECTION
FORMULA
• Any –OH group at a chiral center that is positioned to the
right of a Fischer formula points down in the Haworth
projection formula (Alpha Anomer) – Oh at C1 is below
(starch are all a-D-glucopyranose – can be digested)
• Any group that is positioned to the left of a Fischer formula
points up in the Haworth projection formula (Beta Anomer)
– B-D-glucopyranose – not digested)
NEWMAN PROJECTION
• Three Dimensional

▪ Glucose and Galactose – C4 epimers (mirror only

on 4th Carbon)
▪ Mannose and Glucose– C2 epimers (mirror only
on 2nd Carbon)

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 OPTICAL ACTIVITY

HEMIKETAL FORMATION
Ketose – anomeric carbon is C2

• Rotation of light – determines whether polarized light will

be shifted to the right or left
o Dextrorotatory – to the right (small letter d)
o Levorotatory – to the left (small letter l)
HEMIACETAL FORMATION
Aldose – anomeric carbon is C1

• Glycoside formation – first carbon interacts with the

hydroxyl group of bn2nd to the last carbon (PCA) and
BIOCHEMICALLY IMPORTANT
produces hemiacetal linkage – transforms into a cyclic
structure either Hemsworth projection or Newmann MONOSACCHARIDES
projection D-GLYCERALDEHYDE AND DIHYDROXYACETONE
CYCLIC STRUCTURE OF MONOSACCHARIDES • Important intermediates in the process of glycolysis – how
we derive ATP from glucose ; metabolism
• Glycolysis Pathway

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 o High level of sugar for several months will interact
with hemoglobin
o HBA1c-glycosylated hgbA1c can be used to keep
tract of glucose for 2 months
o Life span of RBC – 120 days
D-GALACTOSE

Glucose and Galactose are different due

to the position of the hydroxyl (OH);
structural configuration
Lactose – disaccharide forme by glucose
and galactose • Synthesized from glucose in the mammary glands for use in
Aldose – anomeric carbon is first lactose (Milk sugar)
Ketose – anomeric carbon is second • A component of glycoprotein found in the brain and nerve
tissues (Brain sugar)
• Present in the chemical marker that distinguish blood types
D-GLUCOSE A, B, AB and O.
• a-D-galactopyranose
D-FRUCTOSE

• a-D-fructopyranose
• Most important in hexoses • Sweetest tasting of all sugars
• Most abundant in nature; tastes sweet; nutritious; important • Found in many fruits (Fruit sugar)
component of the human diet • Optically active; rotates plane of polarized light to the left
• High in grapes (Grape sugar) (Levulose)
• Used by cells as the primary source of energy • Present in honey in equal amount with glucose
• Measured in Blood sugar determination • Used as a dietary sugar
• Optically active; rotates the plane polarized light to the right • Glucose + Fructose = Sucrose
(Dextrose – term used in hospital) • Levorotatory
HBA1c- glycosylated hgbA1c DEOXYRIBOSE
• A component of DNA molecule
• Glycosylated hemoglobin A1c – checked for diabetes
• Lacks an oxygen atom at C2 (deoxygenated)
• Keeping track of blood glucose levels
• Amadori product
D-RIBOSE
• A component of RNA and energy rich compounds such as
• If hemoglobin is exposed to too much glucose sugar, they
ATP – D-Ribose is its component; energy currency of the
interact and form an intermediate Schiff base Amadori
cell; nucleotide
Reaction – sugar is not enzymatically linked to hemoglobin
• 5-carbon atom

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D-RIBOSE AND DEOXY-D-RIBOSE
REDUCTION TO PRODUCE SUGAR ALCOHOLS
• Name of sugar ends with -ol
• Sucrose – non-reducing sugar
• Maltose and Lactose – reducing sugar
o Reduction of Glucose to Glucitol

REACTIONS OF MONOSACCHARIDES
OXIDATION REACTION TO PRODUCE SUGAR
ACIDS
Use oxidizing agent

D-GLUCITOL (D-SORBITOL)
• Used as a sweetening agent in chewing gum
• Used as a moisturizing agent in foods and cosmetics
• Has a high affinity for water
• Accumulation in the eye is a major factor in the formation of
cataracts due to diabetes mellitus
• If blood sugar is uncontrolled, glucose enters the eyes and
gets converted to glucitol that leads to cataract.
• For galactose=Galactitol/Dulcitol
o D-Glucose GLYCOSIDE (ACETAL) FORMATION
▪ If first carbon is oxidized, it will become gluconic
▪ If last carbon is oxidized, it will become uronic
▪ If both carbon is oxidized, it will become aldaric
• weak oxidizing agents
• strong oxidizing agents
• by enzymes
• Oxidized Forms of Glucose:

• Amino sugar formation – add an amino group

o glucose + amino = glucosamine Key concepts:
o galactose + amino = galactosamine • Reducing sugars
• Testing for the Presence of Reducing Sugar o sugars that can be oxidized by mild
o The common oxidizing agents used to test for the oxidizing agents.
presence of a reducing sugar (to know if breducing or o give a positive test with
non-reducing): Tollen’s/Benedict’s/ Fehling’s solutions
• All monosaccharides are reducing sugars.

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• Glycosides - Widely distributed and are present in certain
spices, vegetables, dyes and drugs (cardiac glycosides and
antibiotics).
AMINO SUGAR FORMATION
• Contains an amino group instead of OH group at the C2
position
• D-glucosamine

• D-galactosamine

PHOSPHATE ESTER FORMATION

• Muramic acid- glucosamines linked to 3 carbon acids

at C1 or C3

• N-acetylneuraminic acid
o otherwise known as “sialic acid”
o Forms C-C bond between C1 of N mannosamine and
C3 of pyruvic acid forming a 9-carbon amino sugar
o Usually bound in the carbohydrate chain of
glycoproteins or glycolipids
o Its removal from the oligosaccharide chains on red cells
causes the reticuloendothelial cells to remove the rbc’s.
o Component of gangliosides

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 LOBRY–DE BRUYN–VAN EKENSTEIN • Lactose (β 1à4 linkage)
TRANSFORMATION
• mechanism whereby enzymes convert one aldose to a
ketose isomer and vice versa with the intermediate formation
of an enediol (unsaturated alcohol). (interconversion of
sugar)
• Aldose-Ketose Formation

• Galactose + Glucose
• Sucrose (α 1à2 linkage)
o Both anomeric carbon are connected (non-reducing
sugar)

EPIMERIZATION

• Glucose + Fructose
• Cellobiose (β 1à4 linkage)
o Found in cellulose; cannot be digested by humans but
can be by termites

DISACCHARIDES
• Glycosidic Bond is the bond that connects monosaccharide
units
• Monosaccharide + Monosaccharide
↓
Disaccharide + H2O • Disaccharide of cellulose
OLIGOSACCHARIDES
• 2-10 monosaccharide units
• Glycoprotein

Key concepts:
• The disaccharides maltose and lactose are
reducing sugars.
• Sucrose is a non-reducing sugar.

• Maltose ( α 1à4 linkage) glucose + glucose

o N-linked – attachment of sugar and protein is with

nitrogen
o O-linked – attachment through oxygen

o 2 glucose by glycosidic bond

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 • Glucocerebroside – glucose + lipids (aceramide) GLUCANS
• Purely glucose in composition
• Starch

• Glycolipids – determine blood group

o Components of starch
▪ Amylose
- 13- 20% of starch
- linear unbranched chain of glucose molecules (α
1,4 linkages) (linear form of starch)
▪ Amylopectin –
- 80 – 85% of starch
- branched chains of glucose molecules (α 1,4
linkages in the chain) with branching every 24 –
30 residues via α 1,6 linkages (branched form of
starch)
• Glycogen (Animal Starch)

o O antigen – age antigen

o A antigen – immunodominant sugar is N-acetyl-
galactosamine
o B antigen – immunodominant sugar: d-galactose
POLYSACCHARIDES
More than 10 monosaccharides
o Highly branched
o Consists of glucose molecules linked by α 1,4 linkages in
the chain with branching points every 8 to 12 residues (α
1,6 linkages)
o Glycemic Index (GI)
▪ Glycemic Index of a starchy food is a measure of its
digestibility, based on the extent to which it raises the
blood concentration of glucose compared with an
equivalent amount of glucose or a reference food
such as white bread or boiled rice.
▪ Glycemic index ranges from 1 ( or 100% - being the
easiest to absorb) for starches that are readily
BIOLOGIC FUNCTIONS hydrolyzed in the small intestine to 0 for those that
• Storage of energy – starch, glycogen inulin, dextrans are not hydrolyzed at all
• Structural component – chitin, cellulose ▪ The extent to which starch in foods is hydrolyzed by
• Protective – mucopolysaccharides amylase is determined by its structure, the degree of
Important parameters that distinguish various polysaccharides crystallization or hydration (due to cooking) and
from each other: The identity of the monosaccharide whether it is enclosed in intact (indigestible) plant cell
repeating unit(s) in the polymer chain. walls)
▪ Higher glycemic index is not healthy and may lead to
HOMOPOLYSACCHARIDE
diabetes
• A polysaccharide in which only one type of monosaccharide
monomer is present.

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• Dextrin – almost same with starch
HETEROPOLYSACCHARIDE
• A polysaccharide in which more than one type of
monosaccharide monomer is present.
• Major Glycosaminoglycans:
o Hyaluronic acid
o Chondroitin sulfate
o Keratan sulfate
o Dermatan sulfate
o Heparin

o Glucose residues linked by α 1,6 linkages with additional

α 1,2 or α 1,3 bonds
o Products of partial or incomplete hydrolysis of starch
• Inulin (Fructosan – purely fructose in composition)
o Prebiotic Fiber

o Consists mainly of fructose units joined by β 2,1 linkages

with a terminal glucose residue (FOS- fructo-
oligosaccharides)
o Used to determine glomerular filtration rate (kidney
function)
o Readily soluble in water
o Not hydrolyzed by intestinal enzymes
o Food for good bacteria (probiotics – pampadami ng good
bacteria)
• Chitin
o Gives rigidity to the exoskeletons of crabs, lobsters,
shrimps, insects and other arthropods
o Cell walls of fungi
o Linear polymer of N-acetylglucosamine in β1,4 linkages
• Cellulose

o Glucose residues joined by β 1,4 linkages

o Major component of vegetable fiber
o Chief constituent of plant cell walls
o Source of bulk in the stool
• Mucopolysaccharides
o Mucus production in stomach
o Protects gastric mucosa from hydrochloric acid produced
in stomach
o Mucus secretion

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