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Biochemistry of Carbohydrates PDF
Biochemistry of Carbohydrates PDF
Biochemistry of Carbohydrates PDF
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
Ketotriose
Ketotetrose
Ketopentose
Ketohexose
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
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)
Neuraminic Acid
Oligosaccharides
Polysaccharides
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 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