Sugars or Saccharides

One of the most abundant compounds of living cells

Carbohydrates

In living cells (plants) -> carbohydrates are made by photosynthesis

- Monosaccharides : C3-C9 - Oligosaccharides : 2-10 units

Carbohydrates
Monosaccharides (biological sugars ose)
Most frequently found in nature: - hexoses (six-carbon sugars) -> glucose and fructose - pentoses (five-carbon sugars) -> ribose

S, R Configuration

2 Enantiomers

Fischer Projection
Highest Oxidation state

Carbohydrates
Monosaccharides (biological sugars ose)
Most frequently found in nature: - hexoses (six-carbon sugars) -> glucose and fructose - pentoses (five-carbon sugars) -> ribose Pyranoside Furanoside

Aldoses

Ketoses

Carbohydrates
Monosaccharides
D-Aldoses in the range of C3-C6

Carbohydrates
Monosaccharides
D-Ketoses in the range of C3-C6

Carbohydrates
Monosaccharides
Stereochemistry

D-Erythrose + L-Erythrose -> Enantiomers

D-Erythrose + D-Threose -> Diastereoisomers D-Erythrose + L-Threose -> Diastereoisomers

D-glucose + L-glucose -> Enantiomers

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Carbohydrates
Monosaccharides
Enolization and Isomerization
Epimerization Epimerization

Base-catalysed in water: -> Epimerization + isomerization

Isomerization

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> glucose

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> glucose

CH2OH O
O CH2OH

CH2OH O

CH2OH O

OH

OH

b
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-Sugars have the -CH2OH group and the anomeric hydroxyl group trans. -Sugars have the -CH2OH group and the anomeric hydroxyl group cis.

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> glucose

Glucopyranoside more stable -> almost 100% in pyranoside form 11

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> ribose

In solution mainly in pyranoside form (76%) In nucleotides (or other combinations) mostly found in furanose form 12

Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> fructose

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Carbohydrates
Monosaccharides
Cyclic hemiacetals + hemiketals -> fructose

In solution mainly in pyranoside form (67%) In combinations mostly found in furanose form 14

Carbohydrates
Monosaccharides
The anomeric center Carbonyl group is planar -> attack of OH from either side possible -> 2 epimeric structures (anomers) Both anomers are in equillibrium in solution Epimer (Anomer)
Epimers: -> anomeric center + highest chiral center -> different configuration (R,S convention) Hydroxyl (OH) on anomeric C Down -> -D-sugars and -Lsugars

-> anomeric center + highest chiral center -> same configuration (R,S convention)
Up -> -D-sugars and -L-sugars

Epimer (Anomer)

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Carbohydrates
Monosaccharides
The anomeric center Carbonyl group is planar -> attack of OH from either side possible -> 2 epimeric structures (anomers) Both anomers are in equillibrium in solution

Epimers: -> anomeric center + highest chiral center -> same configuration (R,S convention) -> anomeric center + highest chiral center -> different configuration

R,R->

S,R-> 16

Monosaccharides
The anomeric center

Carbohydrates

Carbonyl group is planar -> attack of OH from either side possible -> 2 epimeric structures (anomers) In solution -> all 4 forms in equillibrium !!!

Aldohexoses Ketose 17

Monosaccharides
The anomeric center

Carbohydrates

Esterfication -> freezes sugar in its anomeric form (no interconvertion between and any more)

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Monosaccharides
Alditols

Carbohydrates

Reduction of sugars -> reducing agent (NaBH4) -> reduces aldehydes + ketons Reduction occurs at small amount of open chain form -> shift in equilibrium -> total reduction achieved Reduction of Aldoses -> 1 product (primary alcohol) -> Alditols Reduction of Ketoses -> 2 products (secondary alcohol) -> Alditols

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) -> Reaction at C1 (anomeric C) Hemiacetals + Alcohol -> Acetals (Glycoside) Hemiketals + Alcohols -> Ketals (Glycoside) OH on the anomeric C1

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) Hemiacetals + Alcohol -> Acetals (Glycoside) Hemiketals + Alcohols -> Ketals (Glycoside)

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) -> Reaction at C1 Hemiacetal/Hemiketal + Alcohol -> O- Glycoside -> Polysaccharides Hemiketal/Hemiketal + Amine -> N-Glycoside

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) Hemiacetal/Hemiketal + Alcohol -> O- Glycoside -> Polysaccharides Hemiketal/Hemiketal + Amine -> N-Glycoside

Template for aspirin

Nucleotides of RNA and DNA

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) Glucose + MeOH -> Acetal -- reaction works directly Glucose + complex alcohol -> not that easy
Example: Production of salicin -> Template for Aspirin

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Monosaccharides

Carbohydrates

Glycosides (replace suffix ose with oside) Glucose + MeOH -> Acetal -- reaction works directly Glucose + complex alcohol -> not that easy
Example: Production of salicin -> Template for Aspirin

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Monosaccharides

Carbohydrates

Cyclic Acetals + Ketals -> protecting groups

2 OH groups are cis conformation -> reaction with keton

C6

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Carbohydrates
Monosaccharides
Modified sugars -> in cell membranes

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Carbohydrates
Oligosaccharides -> a few monomers

Found in dietary products

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Carbohydrates
Polysaccharides

In Plant cell wall -> cotton

In animal and plant cells 29

Carbohydrates
Polysaccharides
Glycogen -> mammalian sugar storage

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Carbohydrates
Polysaccharides
Starch: amylose + amylopectine -> main plant food reserve

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Carbohydrates
Polysaccharides - Hydrolysis

1.

Chemically: - under harsh conditions: with hot acid -> monosaccharides (glucose) - under mild conditions: with acid -> oligosaccharides (randomly)

2. Enzymatic: very specific hydrolysis -> -amylase -> hydrolysis 1 -> 4 bonds in starch (mainly maltose + glucose) -> -1,6-glucosidase -> hydrolysis 1 -> 6 bonds in starch -> lactase -> hydrolysis lactose (high activity of enzyme in infants low activity in adults -> intolerance) -> cellulase -> hydrolysis 1 -> 4 bonds -> animals do not have it (need bacteria)

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Carbohydrates
Oxidation of sugars
Under mild conditions -> with cupric ion (Fehlings solution) or Br2 -> oxidation of aldehyde group -> acid (aldonic acid) If sugars are glycosidic linked (acetal formation) -> aldehyde group not available for oxidation -> no reducing sugars If sugar are free -> reducing sugars

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Carbohydrates
Oxidation of sugars
Under strong conditions -> with HNO3 -> oxidation of aldehyde group + alcohol groups (primary alcohol) -> diacid (aldaric acid)

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Carbohydrates
Oxidation of sugars
Determination of glucose level in blood or urine -> oxidation of glucose > H2O2 involved in second reaction -> colorimetric or voltametric sensor (Biosensor) Diabetes mellitus: Insulin deficiency Insulin regulates blood sugar (glucose) level If glucose level is high -> insulin level increases -> prevents break down of glycogen into glucose and conversion of fat or protein into glucose -> blood glucose level will sink again If glucose level is low -> insulin level drops -> more glucose produced -> blood glucose level will rise

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Carbohydrates
Oxidation of sugars
Terminal OH group oxidized in Aldoses -> Uronic acids Also oxidized by most enzymes

Pectins: in cell walls of fruits -> acid solutions form gels -> jam making

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Carbohydrates
Oxidation of sugars
Terminal OH group oxidized in Aldoses -> Uronic acids Pain reliefer Even stronger pain reliefer

Morphine metabolism in human body -> make it more soluble -> excretion

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Oxidation of sugars

Carbohydrates

Vitamin C: most animals can synthesize Vitamin C Humans and primates cannot NOT -> synthesized in liver from glucose Essential for: - formation of structural proteins in skin, bones, ligaments - cofactor in synthesis reactions of amino acids and modifications - antioxidants

Deficiently (scurvy) -> muscular pain, skin lesions, fragile blood vessel, bleeding gums, tooth loss

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Aminosugars

Carbohydrates

Replacement of one OH group by a amino group In nature -> done by enzymes -> 2-amino-2-deoxy sugars

Chitin: insect skeleton and shells of crustaceans

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Aminosugars

Carbohydrates

Replacement of one OH group by a amino group In nature -> done by enzymes -> 2-amino-2-deoxy sugars Bacterial cell walls -> glycycosidic bond cleaved by lysozyme

Lysozyme

-lactam antibiotics -> inhibit peptidase linking peptide bond during biosythesis of cell wall 40

Aminosugars

Carbohydrates

Replacement of one OH group by a amino group In nature -> done by enzymes -> 2-amino-2-deoxy sugars

Blood groups: Determined by glycoproteins

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