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BIOCHEMISTRY OF CARBOHYDRATES

UST FMS
General Formula: Cx(H2 O)y or (CH2 O)n
Carbon compounds having Carbonyl Carbon (C=O) and hydroxyl ( -OH) functional groups
Carbonyl Functional Groups:
st
Aldehyde (Polyhydroxyaldehydes): 1 C (C=O)
nd
Ketone (Polyhydroxyketones): 2 C (C=O)
Classification
1) Size of base Carbon chain
Triose (3C), Tetrose (4C), Pentose (5C), Hexose (6C), Heptose (7C), Nanose (9C)
2) Number of sugar units
Monosaccharide 1 CHO unit
Disaccharide 2 CHO units
Oligosaccharide 3-10 CHO units
Polysaccharide >10 units
3) Location of Carbonyl carbon
Aldose
Ketose
Nomenclature

Aldotriose

Aldotetrose

Aldopentose

Aldohexose

*Aldohexoses: ALL ALTruists GLadly MAke GUm IN GALlon TAnk.


2 nd C: alternate OH
3 rd C: alternate OH by 2
4 th C: 1 st 4 Right OH, Last 4 Left OH
5 th C: all OH at right side Ketoses

Ketotriose

Ketotetrose

Ketopentose

Ketohexose

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Fischer Projection
Sugars drawn in straight chain
Perspective structural formula: 3D Fisher
Haworth Projection
Cyclic forms which show the molecules as cyclic and
planar with substituents above or below the ring
Boat and Chair conformation: more plausible bent forms
Fischer projection Haworth projection
Optical Activity
Ability to rotate plane of polarized light
All CHOs contain assymetrical (chiral) carbon and are, therefore,
optically active.
a. Dextrorotatory (+): D isomer
o Rotates to right
o In Fischer, -OH is at the right side of penultimate Carbon
o In Haworth, last Carbon is above the ring
b. Levorotatory (-): L isomer
o Rotate to left
o In Fischer, -OH is at the left side of penultimate Carbon
o In Haworth, last Carbon is below the ring
*Assymetric or Chiral Carbon: carbon with 4 different substituents
*Penultimate Carbon: chiral carbon farthest from functional group

Stereochemistry
Isomers: same molecular formula and bonds but differ in spatial arrangement
A. Constitutional Isomers
Different atom connectivities
B. Stereoisomers
Same atom connectivity, different spatial arrangement
2 types: Configurational and Conformational
1. Configurational Isomers
o Interconverted only by breaking covalent bonds (separable)
o 4 types: Enantiomer, Diastereomer, Epimer, Anomer
a. Enantiomer
Stereoisomers which are non-superimposable mirror images of each
other (Eg. D-glucose and L-glucose)
b. Diastereomer
Stereoisomers which are non-superimposable non-mirror images of
each other (Eg. D-galactose and D-glucose)

c. Epimer
Stereoisomers which differ in one stereocenter (different -OH
position along 1 Carbon atom only)
Example: D-glucose, D-mannose and D-galactose
d. Anomer
Stereoisomers which differ only in the configuration around the
carbon (anomeric carbon, usually C1) which was involved in the
intramolecular nucleophilic attack (Eg. and anomers)
Fischer Projection:
anomer (Cis): OH of anomeric Carbon and hemibridge on same side
anomer (Trans): OH of anomeric Carbon and hemibridge on opposite side
Haworth Projection:
anomer (Trans): C6 up, -OH of C1 (anomeric carbon) down if in D isomer
C6 down, -OH of C1 (anomeric carbon) up if in L isomer
anomer (Cis): C6 up, -OH of C1 (anomeric carbon) up if in D isomer
C6 down, -OH of C1 (anomeric carbon) down if in L isomer
*Mutarotation: and are in equilibrium

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2. Conformational Isomers
o Related by rotation around single bond (bending
and twisting)
o Interchange without breaking covalent bonds
o Boat and Chair conformation
a. Boat conformation: less stable due to steric
hindrances
b. Chair conformation: more stable
*Axial Bond: perpendicular to plane
*Equatorial Bond: parallel to plane

Monosaccharides

Glucose
Central sugar in metabolism
Can cyclize through intermolecular nucleophilic attack of one of
the OHs on the Carbonyl Carbon of the aldehyde
Occurs if stable 5 or 6 member rings can form
Furanose (5 member) or Pyranose (6 member)
On nucleophilic attack to form the ring, carbonyl O becomes an OH
Fructose: 67% pyranose, 33% furanose
Ribose: 25%pyranose, 75% furanose
* Glucose is exclusively pyranose. Fructose and Ribose are exclusively furanose.

Monosaccharide Derivatives

1. Sugar Acids
Oxidized forms in which aldehyde and/or alcohol functional groups are oxidized to carboxylic acid ( Oxidation)
a. Aldonic Acid
o Aldehyde group is oxidized (Eg. Gluconic Acid)
b. Uronic Acid
o Terminal alcohol is oxidized (Eg. Glucuronic Acid )
c. Aldaric Acid
o Both aldehyde and terminal alcohol are oxidized
2. Sugar Alcohol
Reduction of Carbonyl group to OH (-ol) (Eg. Dulcitol:
excess causes cataract in galactosemia patients)
3. Phosphorylated Sugar
Phosphate is added by ATP forming phosphoester
derivatives
Eg. Glucose-6-Phosphate Glucose-6-Phosphate
4. Amino Sugars
Amino group replaced hydroxyl group (-OH to -NH)
Eg. Glucosamine, Galactosamine
5. Acetylated Amine Derivative
Sugars derived from amino sugars
Eg. N-acetylglucosamine, N-acteylgalactosamine
6. Lactone Forms
Intramolecular esters
Hydroxyl group attacks Carbonyl carbon that was previously oxidized
to Carboxylic acid (Eg. Gluconolactone)
7. Deoxysugars
One or more Carbon atoms have been reduced, losing hydroxyl
group (-OH to -H) (Eg. Deoxyribose)

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8. Condensation Products of Sugar Derivatives with Lactate and Pyruvate
Forms Muramic Acid (glucosamine + lactic acid)
Forms Neuraminic Acid (mannosamine + pyruvic acid)
N-acetylmuramic Acid (MurNAc or NAM): GlcNac + lactic acid (ether link at C3)
o found in bacterial cell walls
Sialic Acids:
o Found on surface of all cells
o Involved in cell contact/communication
o Involved in recognition bacteria (cholera) and viruses (influenza)
o N-acetyl-neuraminic Acid (NANA):
N-acetylmannosamine (ManNac) + pyruvic acid
found only in humans
lack hydrolase gene (92 base pairs of gene missing)
o N-glycoyl-neuraminic Acid: N-glycoylmannosamine + pyruvic acid
Have hydroxylase

Neuraminic Acid

Oligosaccharides

Polysaccharides

Homopolysaccharides: polysaccharides with 1 type of repeating monosaccharide unit


Starch: found in plants; composed of:
o Amylose (20%)
Linear chain of Glc in 1-4 links (or repeating maltoses)
o Amylopectin (80%)
Branched chain in 1-6 links
o Major part: Glc chain of 24-30 units (amylose) then branches
off (amylopectin)
Glycogen
o Main carbohydrate storage in animals
o Composed of Glc residues in 1-4 links and 1-6 branches
(greater than starch)
o Synthesized on Glycogenin protein primer
o Reason why glycogen is stored rather than glucose: Has less osmotic pressure than glucose, therefore, does not easily
reacts with water
o Source: Muscles (greatest source in terms of total glycogen mass source) and liver (greatest source in terms of grams
glycogen per gram tissue)

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Cellulose
o Linear chain of Glc residues in 1-4 links (or repeating cellobiose)
o Held together by intra- and inter-chain H-bonds
o Most abundant biological molecule in nature; cannot be broken
down by humans (lack of cellulase)
Chitin
o Linear chain of GlcNAc in 1-4 links
Heteropolysaccharides: polysaccharides with 2 different monosaccharide units
Complex Oligosaccharide Units
Mucopolysaccharide s/Glycosaminoglycans (MPS/GAG)
o Amino sugar + negatively charged sulfate or
carboxyl group (uronic acid: glucuronic or iduronic
acid)
o Form matrix to hold protein component of skin,
connective tissue and extracellular matrix
o Often covalently attached to proteins to form
proteoglycans
o Hyaluronic Acid Hyaluronic Acid Dermatan Sulfate
Glucuronate(1-3)GlcNAc
Water soluble; found in synovial fluid
Backbone for attachment proteins
o Dermatan Sulfate
L-Iduronate(1-3)GalNAc-4-Sulfate
o Chondroitin Sulfate
D-Glucoronate(1-4)GalNAc-4or6-Sulfate
o Heparin
D-Glucoronate-2-Sulfate(1-4)GlcNSulfo-6-Sulfate Chondroitin Sulfate Heparin
Antithrombin, naturally-occurring anticoagulant
o Keratan Sulfate
D-Gal(1-4)GlcNAc-6-Sulfate
No uronic acid component
o Syndecan Heparan Sulfate
Binds through intracellular domain to the cytoskeleton
Interacts with fibronectin
o Glypican Heparin Kera ta n Sul fa te
Attached to outer surface of plasma membrane via
phosphatidyl inositol lipid
Peptidoglycans
o Bacterial Cell Walls
Offer protection from hypotonic condition and high internal osmotic
pressure
Long chain of GlcNAc(1-4)MurNAc (NAG,NAM)
Gram (+) Bacteria
Multi-layered; cell wall can be Gram stained (violet)
Chains are covalently connected by a Pentaglycine Bridge through the
-Amino group of tetrapeptide Lysine on one
strand and D-Alanine on another strand
Teichoic Acid
Alternating residue of D-Ala and NAG in C2 Glycerol
or Ribitol Phosphate backbone
Multiple glycerols are linked through Phosphodiester
Bonds
Often attached to C6 of NAM
Make up 50% of cell wall dry weight
Present a foreign antigenic surface to infected host
Serve as receptors for bacteriophages

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Gram (-) Bacteria
Cell wall cannot be Gram-stained (red)
No pentaglycine bridge; chains are connected by direct amide bond between the -Amino group of
tetrapeptide Lysine on one strand and D-Alanine on another strand
Hydrophobic protein covalently attaches (through Lys amide bond) to the last amino acid in the tetrapeptide
unit of cell wall (actually diaminopimelic acid/DAP, which replaces 10% of D-Ala in cell wall)
No teichoic acid; Cell wall sandwiched between lipid bilayer; Periplasmic space space between lipid bilayers
Lipopolysaccharide (O antigen) coats the outer membrane and determines antigenicity of bacteria
Proteoglycans
o GAG covalently O-linked to protein (usually to Ser residue
of Ser-Gly dipeptides)
o May contain N-linked oligosaccharide groups
o Carbohydrates > Proteins
o Soluble
o CHO part provides an incredible variety of binding
structures (acts linke glue) in connecting intra- and
extracellular cell functions
o Syndecan: protein + heparin sulfate + chondroitin sulfate;
binds through its intracellular domain to the internal
cytoskeleton of the cell while interacting with fibronectin
in the extracellular matrix
o Aggrecan: protein + Chondroitin sulfate + Keratan sulfate; binds hyaluronic acid; important in hydration of cartilages
o Versican: protein + Chondroitin sulfate; binds hyaluronic acid in extracellular matrix
Glycoproteins/Glycosylated Proteins
o Proteins post-translationally modified by attachment of carbohydrates
o Usually attached through either Asn or Ser side chains
o Involved in recognition of binding molecules, prevention of aggregation
during protein folding, protection from preoteolysis , increase in protein
half-life, blood clotting, immunologic protection and ABO blood groups.
o N-linked glycoproteins
Carbohydrate attached to either GlcNAc or GalNAc to an Asn in a X -
Asn-X-Thr sequence of protein
Core oligosaccharide: (Man)3 (GlcNAc)2 attached to Asn
3 types: Mannose, Complex, Hybrid
o O-linked glycoproteins
Carbohydrate usually attached from a Gal(1-3)GalNAc to a Ser or
Thr of a protein
Eg. Blood Group Antigens
Storage Polysaccharides: Starch, Glycogen
Structural Polysaccharides: Cellulose, Chitin, GAGs, Peptidoglycans

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Hemiacetal and Hemiketal Formation

Aldehyde or ketone group of monosaccharides can cyclize through intramolecular nucleophilic attack of a hydroxyl group ( -OH)
at the Carbonyl carbon in an addition reaction forming Hemiacetal or Hemiketal, respectively.
On addition of acid: anomeric OH is protonated, forming water, a leaving group
Another alcohol can be added forming Acetal or Ketal

Reducing Property of Sugars

Reducing Sugars: sugars which can form an aldehyde at C1 or have an -hydroxymethyl ketone group which can isomerize
to an aldehyde under basic conditions, such as fructose
o Eg. All common monosaccharides, maltose
o Eg. Lactose: Since Glc is attached through the OH on C4, its anomeric carbon could revert to noncyclic aldehyde form,
which is susceptible to oxidation , thus, subsequently reduced.
Non-Reducing Sugar: sugars in which there are no aldehyde or ketone group to react; sugar rings are locked or not capable
of opening
o Eg. Sucrose: Since the anomeric carbons of both Glc and Fru are linked, it cannot be reduced (neither of the rings can
be opened).
Tests for identifying Reducing Sugars:
o Benedicts: Copper Sulfate + Alkaline Citrate; deep blue brick red ppt
o Fehlings: Copper Sulfate + Alkaline Tartrate; deep blue brick red ppt
o Tollens: Silver Nitrate + Aqueous Ammonia; colorless silver mirror

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