BIOCHEMISTRY (LECTURE) MONOSACCHARIDE CLASSIFICATION: FUNCTIONAL

GROUP
5. CARBOHYDRATES
ALDOSE KETOSE
INTRODUCTION
Contains an aldehyde group. Contains a ketone group.
- Hydrate (H2o) of carbon (C). Example: Glyceraldehyde Example: Dihydroxyacetone
- Formula:
o CₙH₂ₙOₙ
o Cₙ(H₂O)ₙ
- Refers to the following:
o Polyhydroxy aldehydes
o Polyhydroxy ketones
o Compounds that can be hydrolyzed to
them.

- (Carbon: # of bonds should be 4.)

- (Oxygen: # of bonds should be 2.)
- (Hydrogen: 1 bond)
- Aldehyde func grp: H--C=O or CHO
o Always found in terminal.
- Ketone: C=O (carbonyl)
o Within the chain.
CLASSIFICATION - (Enzyme: -ase; Carbs: -ose)
- (Simplest aldose: Contains 3 carbons)
CATEGORY DESCRIPTION EXAMPLE - (Simplest ketose: Carbonyl group is within the
Monosaccharide Has a single polydroxy Glucose, chain.)
aldehyde or Fructose
polyhydroxy ketone. MONOSACCHARIDE CLASSIFICATION: NO. OF C ATOMS
Oligosaccharide 2-10 monosaccharide Sucrose No. of Carbons Name Example
units covalently (disaccharide), 3 Triose Glyceraldehyde
bonded to each other. Lactose 4 Tetrose Erythrose
5 Pentose Ribose
Polysaccharide Has several thousand Cellulose Glucose, Fructose,
6 Hexose
monosaccharide units. Galactose, Manose
7 Heptose Sedoheptulose
- Sugar is a general designation for either a
monosaccharide or disaccharide.
- (Proteins: Amino Acids; Carbs:
Monosaccharides)
- GLUCOSE: Product of photosynthesis.
- OLIGO: few; POLY: many or plenty
- SUCROSE: Table sugar
- CELLULOSE: found in plants; humans doesn’t
have this.
MONOSACCHARIDES: OVERVIEW
- A carbohydrate that cannot be hydrolyzed to
simpler compounds.
o White BACKTRACK: CHIRALITY
o Crystalline solid
o All are sweet tasting - (Should have 4 DIFFERENT attached atom or
o Polar compounds with high melting group of atoms.)
points. - Chiral Molecule
o Water soluble o A molecule whose mirror images are
o Insoluble in organic solvents like not superimposable.
diethyl ether. - Glyceraldehyde
- (Basic units that comprises carbs.) o There are 2 possible enantiomers.
- CLASSIFICATION:  D/L
o Based on functional group.  D dominates.
o Based on the number of carbon atoms.  (Amino acid: Amine; Carbs:
Hydroxyl group)
o (C2 is chiral)
D-Glyceraldehyde (common) D & L MONOSACCHARIDES
L-sugar D-sugar
The OH group on the The OH group on the
stereogenic (chiral) center stereogenic (chiral) center
farthest from the carbonyl farthest from the carbonyl on
on the left in a Fischer the right in a Fischer
projection. projection.

L-Glyceraldehyde (uncommon)

- The configuration of the stereogenic center

farthest from the carbonyl group determines
To Know Whether to Put D or L: whether a monosaccharide is D- or L-.
- Glucose and all other naturally occurring
- Find the functional group (aldehyde) – C1 sugars are D- sugars.
- Locate the farthest carbon from your functional
group that is chiral OR the second to the last
carbon. – C5
- Know the position of hydroxyl group (-OH)
o Left: L
o Right: D
CARBOHYDRATES: PROJECTIONS
- (Projection = Representation; how u represent
carbs structure.)
- Fischer Projection
- (ENANTIOMER: Structures that are mirrored
o Used when you have a carbs structure
image of each other but are not
that is in an OPEN-CHAIN.
superimposable.)
o Superimpose = ipapatong
D-ALDOSES (FISCHER PROJECTION)

- Haworth Projection
o Used when the structure is in RING
FORM/CYCLIC.
o Enclosed figure.
CARBS PROJECTION: FISCHER
- Numbering: The most oxidized end of the
molecule has the lowest number.
o Many (>1) oxygen.
o Has double bond (=).
D-KETOSES (FISCHER PROJECTION)

Epimer
- 2 sugars that differ in configuration around 1
specific carbon atom.

STEREOISOMERS
- (You’ll observe kung saang carbon nagkaron ng
pag-flip or nagbaligtad yung position ng
hydrogen at hydroxyl group.)
- (D-Galactose: An EPIMER of D-Glucose at C4.)
o CONSEQ: From the structure of glucose
alone, you can generate the structure
of galactose.)
Anomer
- Hemiacetals or hemiketals which differ only in
configuration at carbon-1 which is the
asymmetric (chiral) center.
o (Hemiacetals: from aldehyde)
o (Hemiketals: from ketone)
o (C1: Anomeric Carbon)
- Its asymmetry is a consequence of
mutarotation.
- (Enclosed figure)

- Diastereomers MONOSACCHARIDE: CYCLIC FORMS

o These are stereoisomers whose
molecules are not mirror images of
each other.
o (Non-superimposable)
o (B: Pair of diastereoisomers)
- (ISOMER: Same molecular formula = CₓHᵧOz)
- (STEREOISOMER: 3-D)
- (CONSTITUTIONAL ISOMER: 2-D)
MONOSACCHARIDE: STRUCTURAL ISOMERS
- Enantiomer
- Epimer
- Anomer
Enantiomer
- Stereoisomers whose molecules are
nonsuperimposable mirror images of each
other.
 - Cyclization always forms a new stereogenic o Phosphate Ester Formation
center (chiral) at the anomeric carbon (C1), so o Amino Sugar Formation
2 different anomers are possible.  (Derivatives: You have a
o 2 different anomers: structure of monosaccharide
 Alpha kaya lang, you are going to
 Beta replace one atom w/ another.)
o (Cyclization: Formation of a ring from
the open-chain.) CHEMICAL PROPERTIES: OXIDATION
o (Pag nagclose ring, may mabubuong - Product: Sugar acids
bagong chiral carbon = C1) o Why acid? Because of the carboxylic
CARBOHYDRATE PROJECTION: HAWORTH acid that you will see on the product’s
functional group.
D Form L Form - Product depends on the point of oxidation:
CH₂OH is positioned above CH₂OH is positioned below o Oxidation at C1
the ring. the ring. o Oxidation at C6
o Oxidation at C1 and C6
- (How do you know it’s oxidation?)
o Increase # of O atoms
o Single bonds > Double bonds

- The D or L form of a monosaccharide is

determined by the position of the terminal
CH₂OH group on the highest-numbered ring
carbon atom. (C6)
- (CH₂OH: Carbon 6)
- (Ring: Find O atom > Baba pakanan = that’s the
C1.)
α Form β Form
CH₂OH and –OH (hydroxyl CH₂OH and –OH (hydroxyl
group in carbon 1) are on group in carbon 1) are on the
opposite sides. same side. - (Tollens Reagent: Silver and ammonia)

CARBOHYDRATES: CONFORMATION
- Designation of Conformations:
o Six-membered ring:
 C-chair (stable)
 B-boat (unstable)
 S-skew or Twist boat - (Presence of brick-red precipitate: Test was
o Five-membered ring: positive; carbs do contain an aldose.)
 E-envelope (stable) - (Benedict’s: Uses citrate as a reagent)
 T-twist - (Fehling’s: Copper (II) Oxide)

MONOSACCHARIDES: REACTIONS
- Oxidation
- Reduction
- Formation of Derivatives - (CH2OH > -COOH - carboxylic)
o Glycoside Formation
o Exhaustive Methylation
 - (Product: Glycoside (O-CH2-CH3) from ethanol
will be added to the position of hydroxyl group
on the reactant side, replacing the H atom.)
- (If Tollen’s, Benedict’s, and Fehling’s reagents
were used > NEGATIVE)
o Why? Because they react only with C1.
MONOSACCHARIDES: AMINO SUGAR FORMATION
- Product: Amino sugar (NH2)
- Most monosaccharide can acquire an amino
group at C2.
- The acquired amino group can be acetylated to
form N-acetyl derivatives.
- (Reagent: Nitric Acid)
- (CHO and CH2OH > COOH – carboxylic acid)
COMPARING USING GLUCOSE

MONOSACCHARIDES: PHOSPHATE ESTER FORMATION

- Substrate: Hydroxyl group of a monosaccharide
- Reagent: Inorganic oxyacids
o (Phosphoric acid: H3PO4)
- Product: Inorganic esters

MONOSACCHARIDES: REDUCTION
- Reagent: NaBH₄
o (Sodium borohydride)
- Product: Sugar alcohol (Alditol)
o 1° alcohol
SUGAR SUGAR ALCOHOL - (Maglalagay ng phosphate group.)
Glucose Sorbitol - (H atom was replaced by a phosphate group at
Galactose Galactitol C6)
Mannose Mannitol FORMATION OF DERIVATIVES: FORMATION OF SUGAR
SULFATES
- (REDUCTION:) - Some polysaccharides contain sulfates
o Increase H atoms. esterified at C2, C4 and/or C6.
o Concerns C1 only. - KS: Found especially in the cornea, cartilage,
 CHO > CH2OH and bone
CHEMICAL PROPERTIES: FORMATION OF DERIVATIVES - DS: Found mostly in skin, but also in blood
vessels, heart valves, tendons, and lungs.
- Glycoside Formation
- Formation of Amino Sugars
- Formation of Sugar Sulfates
MONOSACCHARIDES: GLYCOSIDE FORMATION
- Substrate: Monosaccharide (hemiacetal)
- Reagent: Alcohol in acid solution
o (HO-CH2-CH3: Ethanol)
- Product: Glycoside (acetal)
o Do not undergo mutarotation.
- Does not react with any of the following:
o Tollen’s
o Benedict’s
o Fehling’s
FORMATION OF DERIVATIVES: FORMATION OF SUGAR - (CONSEQUENCE: Paggamit ng hydroxyl group
SULFATES (cont.) to form glycosidic bond; wala nang H atom = it
becomes the NONREDUCING END)
- The sulfate group is negatively charged at o WHY? Kasi hindi na pwedeng
physiological pH. makapagreact ang O atom sa iba pang
- C4S: An important structural component of incoming na sugar; Nonreactive na siya
cartilage and provides much of its resistance to – may glycosidic bond na kasi, gamit na
compression. - (Reducing end: Buo pa yung hydroxyl group;
pwede pang makapagform ng glycosidic bond;
pwede pang mag-undergo ng reaction.)
- (GLC: Glucose; Pyranosyl: has 6-membered
ring)
DISACCHARIDES: OVERVIEW
- Maltose
- Cellobiose
- Lactose
- Sucrose
DISACCHARIDES: FORMATION

- (Part that combines: Anomeric carbon of

glucose + One of the carbons of fructose =
water molecule will be one of the products.)
DISACCHARIDES: DISTINGUISHING FEATURES
- (MAIN PRODUCT: Formation of disaccharide)
- The 2 specific sugar monomers involved and
DISACCHARIDES: SUCROSE (table sugar)
their configurations:
o Sucrose: D-glucose and D-fructose - Monosaccharide units: α-D-glucose and β–D-
o Maltose: D-glucose fructose
- The order of the 2 monomer units, if they are - Glycosidic linkage: α,β(1→2)
different kinds: - Only 1 form exists in either the solid state or in
o Lactose: D-galactose + D-glucose solution.
- The anomeric configuration of the hydroxyl - Undergoes hydrolysis – broken into 2 (through
group on C1 of each residue. sucrase or acidic condition).
- The carbons involved in the linkage: - Non-reducing sugar.
o Sucrose: 1→2
o Trehalose: 1↔1
o Lactose: 1→4
DISACCHARIDES: WRITING THE STRUCTURES
- The sequence is written starting with the
nonreducing end at the left.
- Anomeric (α/β) and enatiomeric (D/L) forms
are designated by prefixes.
- EXAMPLE:
o α–D-Glucopyranosyl-(1→4)-β-D-
glucopyranose
- The ring configuration is indicated by a suffix o (In reference with Tollen’s Benedict’s,
o [α-D-Glcp-91→4)-β-D-Glcp] (for and Fehling’s tests.)
maltose)
- The atoms between which glycosidic bonds are SUCROSE: INVERSION
formed are indicated by numbers in - There is a change in the direction of rotation of
parentheses between residue designations. plane-polarized light.
- Catalyzed by invertase (enzyme)
- Direction:
o (+) clockwise for sucrose
o (-) counterclockwise for invert sugar

- (Proteins: Peptide Bond; Carbs: Glycosidic

Bond)
 DISACCHARIDE: MALTOSE (malt sugar)
- Monosaccharide units: two D-glucose
- Glycosidic linkage: α(1→4)
- Reducing sugar
- Undergoes mutarotation
- Undergoes hydrolysis (through maltase or
acidic condition) - (Used as thickening agents.)
POLYSACCHARIDES: KEY FEATURES
- Identity of the monosaccharide repeating
unit/s in the polymer chain.
- Length of the polymer chain.
- Type of glycosidic linkage between monomer
units
- Degree of branching of the polymer chain.
POLYSACCHARIDES: BIOLOGICALLY IMPORTANT
- (Can be found in plants – barley) - Storage polysaccharide
- (Pyranose: In ring form) o Starch
o Glycogen
DISACCHARIDES: LACTOSE (mlik sugar) - Structural polysaccharide (support)
- Monosaccharide units: α-D-glucose and β–D- o Cellulose
galactose o Chitin
- Glycosidic linkage: β(1→4) - Acidic polysaccharide
- Reducing sugar o Hyaluronic acid
- Undergoes mutarotation o Heparin
- Undergoes hydrolysis (through lactase or acidic - (They play a major role sa mga living
condition) organisms.)
POLYSACCHARIDES: STORAGE
- EXAMPLES:
o Starch (plants only)
o Glycogen (humans and lower forms of
animals)
- FUNCTION:
o Energy source in cells.
POLYSACCHARIDES: STARCH
β-D-galactopyranosyl-(1→4)-D-glucose - Homopolysaccharide
o (HOMO: pinagdugtong-dugtong yung
- (Lactose intolerant: They don’t have enzyme to monosaccharide pero isang klase lang
degrade this.) siya.)
- Identity of monosaccharide repeating unit:
DISACCHARIDES: CELLOBIOSE (cellulose)
Glucose
- Monosaccharide units: two D-glucose - Has nutritional value for humans.
- Glycosidic linkage: β(1→4) - Can be detected by the iodine test.
- Reducing sugar - Contains the following:
- Can exist in 3 forms in aqueous solution o Amylose
- Undergoes hydrolysis (through cellobiase or o Amylopectin
acidic condition)

POLYSACCHARIDES: STARCH (AMYLOSE)

POLYSACCHARIDES: OVERVIEW
- Identity of monosaccharide repeating unit:
- Contains many monosaccharide units bonded Glucose
to each other by glycosidic linkages. - Glycosidic linkage: α(1→4)
- Not sweet
- Yields negative results in Tollen’s and
Benedict’s solutions.
- Have limited water solubility.
- The –OH groups present can individually
become hydrated by water molecules.
 - Structure: Has a spiral-like structure POLYSACCHARIDES: STARCH & GLYCOGEN
- Length of the polymer chain: 300-500
monomer units.
- Degree of branching: None because it’s linear.
- Amount: 15%-20% of the starch is in this form.

- (Mas maraming branches ang glycogen than

starch.)
o Since mas complex ang ginagawa
natin, being a higher form of being,
dapat mas marami talagang
makuhaan ng energy in a short span of
POLYSACCHARIDES: STARCH (AMYLOPECTIN) time. This is possible only if mas
- Identity of monosaccharide repeating unit: maraming branches than amylopectin.
Glucose - (Starch: In plants; Glycogen: In humans,
- Glycosidic linkage: α(1→4) and α(1→6) animals)
- (More frequent branching = Mas maraming
dulo yung pwedeng ma-cleave in a short period
of time = Mas madali kagad matutugunan yung
energy requirement ng organism at that
specific time.)
POLYSACCHARIDES: STRUCTURAL
- EXAMPLES:
o Cellulose
o Chitin
- FUNCTIONS:
- Length of the polymer chain: up to 100,000
o Structural element in plant cell walls.
glucose units
(cellulose)
- Degree of branching: A branch occurs about
o Exoskeletons in animals. (chitin)
once every 25-30 glucose units.
- Amount: 80%-85% of the starch is in this form. POLYSACCHARIDES: CELLULOSE
- Water-insoluble (general property of
polysaccharides)
- Fibrous
- FUNCTIONS:
o Structural component of plant cell
walls.
o A source of nutrition.
o As a dietary fiber.
o Has a role in weight control.
- (Cotton: 95% cellulose; Wood: 50%)
- Homopolysaccharide
POLYSACCHARIDES: GLYCOGEN - Identity of monosaccharide repeating unit:
Glucose
- Homopolysaccharide - Glycosidic linkage: β(1→4)
- Identity of monosaccharide repeating unit: - Structure: Linear
Glucose
- Glycosidic linkage:
o α(1→4) – for main chain
o α(1→6) – used for branching

- Length of the polymer chain: About 5,000

monomer units.
- Length of the polymer chain: up to 1,000,000 - Degree of branching: Unbranched
monomer units. - Molecular mass: About 900,000 amu
- Degree of branching: A branch occurs about
once every 8-12 glucose units.
o (Branching here is more frequent than
amylopectin.)
POLYSACCHARIDES: CHITIN o Associated with the jelly-like
consistency of the vitreous humor of
- FUNCTIONS: the eye.
o To give rigidity to the exoskeletons of
crabs, lobsters, shrimp, insects, and
other arthtopods.
o As cell walls of fungi.

POLYSACCHARIDES: HEPARIN
- Heteropolysaccharide
- Identity of monosaccharide repeating unit:
- Homopolysaccharide o D-glucuronate-2-sulfate
- Identity of monosaccharide repeating unit: N- o N-sulfo-D-glucosamine-6-sulfate
acetyl-α-D-glucosamine - Glycosidic linkage: α(1→4)
- Glycosidic linkage: β(1→4)
- Structure: Linear

POLYSACCHARIDES: ACIDIC - Length of the polymer chain: 15-90

disaccharide units per chain
- (Being acidic has something to do with the - Degree of branching: Unbranched
oresence of the functional group: COOH) - FUNCTION: An anticoagulant
- EXAMPLES: o (Reverse of blood clot)
o Hyaluronic Acid
o Heparin CARBOHYDRATE: DIETARY CONSIDERATIONS
- FUNCTION: SIMPLE CARBOHYDRATE COMPLEX CARBOHYDRATE
o Involved in a variety of cellular Dietary monosaccharide or Dietary polysaccharide
functions and tissues. disaccharide
POLYSACCHARIDES: HYALURONIC ACID Sweet to the taste Not sweet to the taste
Natural sugar: Milk, Fresh Starch and cellulose
- Heteropolysaccharide fruit
- Identity of monosaccharide repeating unit: Refined sugar: Sugar cane
o N-acetyl-β-D-glucosamine - (Natural: It is part of mixtures of substances
o D-glucuronic acid obtained from a plant source.)
- Glycosidic linkage: alternating β(1→3) and - (Refined: Separated from its plant source)
β(1→4)

- Length of the polymer chain: Approximately

50,000 disaccharide units per chain.
- Degree of branching: Unbranched
- FUNCTIONS:
o Serves as lubricants in the fluid of
joints.