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09 Carbohydrates

09 Carbohydrates

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Published by Eric Owen Yeates

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Published by: Eric Owen Yeates on Jun 12, 2012
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Carbohydrates

Structure of Carbohydrates

CH2OH O O—H HO OH OH

CH2OH O OH H2O

CH2OH O O

CH2OH O OH

H—O OH OH

HO OH OH

OH OH

Sugars

Oligosaccharides Polysaccharides

Properties of Carbohydrates
• Most abundant class of organic molecules • Source: Photosynthesis • Nomenclature
– Suffix: -ose – Classification
• Monosaccharides • Oligosaccharides (2- ~20 sugars) • Polysaccharides (> ~20 sugars)

Biological Roles of Carbohydrates
• • • • Energy source Energy storage Cell walls Recognition events – Between proteins – Between cells • Signalling • Components of other biological molecules – Antibiotics – Enzyme cofactors – Nucleic Acids

Monosaccharides (Sugars) .

Classes of Monosaccharides Aldoses (Aldehydes) H C H C OH O CH2OH C O Ketoses (Ketones) CH2OH CH2OH D-Glyceraldehyde Dihydroxyacetone .

versus L.Chirality H C H C OH OH O H C C H O CH2OH CH2OH D-Glyceraldehyde L-Glyceraldehyde D.determined by chirality of highest number carbon (from aldehyde or ketone) .

Aldoses Figure 8-1 .

Enantiomers (mirror images) O C H HO H H C C C C OH H OH OH HO H HO HO H C C C C C H OH H H H O CH2OH D-Glucose CH2OH L-Glucose .

(stereoisomers differing by configuration of only one of several chiral centers) H C H HO H H C C C C OH H OH OH HO HO H H O H C C C C C H H OH OH H HO HO H O H C C C C C OH H H OH O Epimers CH2OH D-Glucose (glc) CH2OH D-Mannose (man) CH2OH D-Galactose (gal) .

(stereoisomers differing by configuration of only one of several chiral centers) H C H HO H H C C C C OH H OH OH HO HO H H O H C C C C C H H OH OH H HO HO H O H C C C C C OH H H OH O Epimers CH2OH D-Glucose (glc) CH2OH D-Mannose (man) CH2OH D-Galactose (gal) .

Ketoses Figure 8-2 .

Mutarotation Creation of new chiral center .

R1 H O R + C O R1 H H H Chiral . O ..Formation of Hemiacetal + H O C R H ..

H R1 R + C O H R1 R2 H O C R Chiral . O ..Formation of Hemketal + H O R2 ..

Anomeric Carbon Atom Mutarotation Reversible Creation of new asymmetric center .

Cyclization of D-Glucose .

Anomers • Anomeric carbon atom – Most oxidized carbon atom  -configuration has -OH on opposite side of ring from CH2OH group (C6) – D-sugars: C6 is above the ring • α  OH group below the ring • β  OH group above the ring .

Cyclization of D-Fructose (biologically relevant forms) HOCH2 O CH2OH OH OH HO H H CH2OH C C C C O H OH OH HOCH2 O OH OH CH OH 2 OH -D-Fructose OH CH2OH -D-Fructose D-Fructose .

Examples of Nomenclature -D-glucopyranose Configuration of anomeric carbon -D-fructofuranose Sugar prefix Ring Type *not required Anomeric carbon modification: ose: reducing oside: non-reducing Configuration of sugar .

Cu(OH)2 Cu2O Cupric oxide brick-red precipitate . can act as reducing agents.Reducing test Free aldehyde can be oxidized.

Chair Conformations of -D-glucopyranose Equatorial Axial Chair and Boat Forms Equitorial and Axial Substituents Steric Crowding: equitorial more stable Figure 8-5 .

Derivatives of Monosaccharides .

6-bisphosphate (Fru-1.Phosphate Esters CH2OPO32– O OH HO OH OH OH =O 3POCH2 O OH OH CH2OPO32– -D-Glucose-6-P (Glc-6-P) -D-Fructose-1.6-bisP) H O C H H C OH H C OH CH2OPO32– CH2OPO32– C OH CH2OH C O H C O CH2OPO32– Dihydroxyacetone phosphate (DHAP) D-Glyceraldehyde 3-phosphate (G3P) D-Erythrose 4-phosphate (E4P) .

Deoxy Sugars HOCH2 O 2–O POCH 3 2 O OH OH OH OH 2-Deoxyribose (dRib) Deoxyribose 5-phosphate (dRib-5-P) [Deoxy--D-ribofuranose 5-phosphate] .

g.Amino Sugars (e. GlcNAc-6-P) CH2OP O OH HO NH C H3C O OH N-Acetyl-D-glucosamine 6-phosphate .

Sugar Alcohols H H C H H H C C C OH OH OH H H H O CH2OH C C C OH OH OH H HO H H C C C C C OH H OH OH H HO H H O CH2OH C C C C OH H OH OH CH2OH CH2OH CH2OH CH2OH D-Ribose Ribitol D-Glucose Sorbitol .

Glycosides .

Structure of Glycosides Monomers (Sugars) Polymerization Polymers (Disaccharides) (Oligosaccharides) (Polysaccharides) NOTE: linear and branched polymers .

Glycosidic Linkages (glycoside) CH2OH O OCH 3 OH HO OH Acetal Stable: no mutarotation Non-reducing sugar (no free anomeric C atom) .

Nomenclature CH2OH O OCH 3 OH HO Optional OH CH3O OH OH OH CH2OH O OH HOCH2 O HO CH2OH OCH3 O-Methyl--DGlucopyranoside [Non-reducing] 4-O-Methyl--DGlucopyranose [Reducing] Methyl--DFructofuranoside [Non-reducing] .

Disaccharides .

-Maltose CH2OH O OH HO OH O OH OH OH __> CH2OH O -D-glucopyranosyl-(l 4)--D-glucopyranose Glc(α14)Glc .

Sucrose (non-reducing) CH2OH O OH HO OH O OH __> HOCH2 O OH CH2OH -D-glucopyranosyl-(l 2)--D-fructofuranoside OR: Glc(α1 β2)Fru .

-Lactose Gal(β14)Glc .

Glycoproteins • Oligosaccharides – Posttranslational modification – Targeting – Recognition – Complex heteropolymers .

O-linked Oligosaccharides (serine/threonine) .

N-linked Oligosaccharides (asparagine) .

Polysaccharides .

Linear Polysaccharides glycosidic linkages non-reducing end (NRE) reducing end (RE) .

Branched Polysaccharides glycosidic linkages NRE RE .

Functions of Polysaccharides • Structural . plant cell walls. glycogen as energy reserves: -linkages are readily cleaved – Solves Potential osmotic problem – Accessibility for energy production • -linkages • Branching .g.e.g. cement between cells (animals): -linkages stable to enzymatic cleavage • Storage .e.

(plant cell walls) Cellulose CH2OH O O OH O CH2OH O OH O OH OH -(1___>4) .

crustacians. and spiders) Cell wall (most fungi and some algae) .(1—>4)-linked homopolymer of N-acetylglucosamine Chitin Exoskeletin of invertebrates (e.g. insects.

Glycogen/Starch (storage) Linear: α14 Branches: α16 CH2OH O OH O OH CH2OH O OH HO OH O OH OH O OH OH CH2 CH2OH O OH O O OH OH OH CH2OH O O CH2OH O OH HO .

but fewer branches) .Starch (plants) linear branched (similar to glycogen.

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