Carbohydrates. mono-, di-, polysachcrides

Сентябрь 9, 2022

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Carbohydrates. mono-, di-, polysachcrides

Содержание

2. PLAN Classification of carbohydrates. Nomenclature. Structural representations be Fisher and Haworth. Chirality. Optical isomers. Tautomerism. Mutarotation.
3. Carbohydrates The term "carbohydrate" was proposed by K.G. Shmidt in 1844. Cn(H2O)m (n=3-9) A carbohydrate is
4. Carbohydrates. Classification. There are two classes of carbohydrates: simple carbohydrates and complex carbohydrates. Simple carbohydrates are
5. Monosaccharide‘s classification. type of the carbonyl group Carbon chain length 3 Carbon - Trioses are not
6. The number of optical isomers: N=2n (number of asymmetric centers) triose tetroses D-glyceraldehyde D-eritrose D-treose Dexter-reference
7. Structure of monosaccharides. Carbonyl and hydroxyl groups of monosaccharides react to form intramolecular hemiacetal:
8. The structure of monosaccharides is presented in three forms: Fisher projection: straight chain representation. 2. Haworth
9. Structure of monosaccharides. β-Hemiacetal hydroxyl α-Hemiacetal hydroxyl Anomeric center Anomeric center D-Glucose β,D-glucopyranose α,D-glucopyranose Dexter OH
10. Hydroxyl group at the anomeric center is called a hemiacetal or glycoside. Diastereomers - stereoisomers that
11. α-Hemiacetal hydroxyl Prospective Haworth formula (1929)
12. Prospective Haworth formula One can remember that the β anomer is cis by the mnemonic, "It's
13. Isomeric transformation of monosaccharides by the action of alkalis is called epimerization. Epimers are called diastereoisomers,
14. Keto-endiol tautomerism Epimerization in alkaline media
15. 1. Intermolecular dehydration Chemical properties Reaction to distinguish pentoses from hexoses.
16. 1. Intermolecular dehydration Chemical properties Reaction to distinguish pentoses from hexoses.
17. Molish test α-naphtol
18. Selivanov’s test
19. 2. Reactions involving aldehyde group Reaction with hydroxylamine (the product with one less carbon atom)
20. Cyanohydrin’s synthesis (the product with one more carbon atom)
21. 3. Reduction diabetic sweeteners
22. 4. a) Oxidation in neutral and mild acidic media b) Oxidation with strong oxidizers
23. c) Oxidation by enzymes
24. Identification of aldehyde group with:
25. 5. Glycosides formation: Glycoside bonds glycone aglycone
26. 6. Acylation: 7. Alkylation:
27. Disaccharides (bioses) Depending on the method of the glycosidic bond formation reducing nonreducing In reducing disaccharide
28. Maltose
29. Cellobiose
30. Lactose
31. Sucrose "Inversion" - a sign change of the specific rotation after the hydrolysis of sucrose. A
32. Sucrose. chemical properties. Doesn’t mutorotate No silver mirror reaction No reactions by aldehyde group Hydrolysing to
33. Amylose 20% Soluble in Н2О Amylopectine 80% Insoluble Н2О Starch hydrolysis Starch. Structure
34. Amylose α-1,4-glycosidic bond Spiral structure
35. Amylose with iodine forms clastrates of dark blue color.
36. Amylopectin α-1,6’-glycosidic bond α-1,4’-glycosidic bond branched structure
37. Cellulose Cellulose hydrolysis β-1,4-glycosidic bond linear structure
38. Hyaluronic acid β-1,3-glycosidic bond β-1,4-glycosidic bond D-glucuronic acid D-N-acetylglucosamine Heteropolysaccharides:
39. Chondroitin sulfate β-1,3-glycosidic bond β-1,4-glycosidic bond D-glucuronic acid D-N-acetylgalactosamine
40. Heparin L-iduronate-2-sulfate N-sulfo-D-glucosamine- -6-sulfate α-1,4-glycosidic bond
42. Скачать презентацию

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PLAN
Classification of carbohydrates.
Nomenclature.
Structural representations be Fisher and Haworth.
Chirality. Optical isomers.
Tautomerism. Mutarotation.
Epimerization.
Chemical

properties:
Identification reactions.
Disaccharides: maltose, galactose, cellobiose, sucrose.
Polysaccharides: starch, hyaluronic acid, chondroitin sulfate, heparin.

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Carbohydrates
The term "carbohydrate" was proposed by K.G. Shmidt in 1844.
Cn(H2O)m

(n=3-9)

A carbohydrate is macromolecule, consisting of carbon, hydrogen, and oxygen atoms, usually with a hydrogen : oxygen atom ratio of 2:1 (as in water) with the empirical formula Cm(H2O)n.
Structurally they are polyhydroxy aldehydesStructurally they are polyhydroxy aldehydes and ketones.

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Carbohydrates. Classification.
There are two classes of carbohydrates:
simple carbohydrates and

complex carbohydrates.
Simple carbohydrates are monosacrharides (2 or more monosachcharides linked together).
Disachcharides have 2 linked monosaccharides.
Oligosacharides have 3 to 10.
Polysaccharides have 10 or more.
Homopolisaccharides consist of the same monosaccharide residues (starch, cellulose, etc.).
Heteropolysaccharides – of different monosaccharide residues (hyaluronic acid, etc.).

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Monosaccharide‘s classification.
type of the carbonyl
group
Carbon chain length
3 Carbon - Trioses

are not saccharides.
4 Carbon - Tetroses are unknown in nature.
5 Carbon - Pentoses
are widely used.
6 Carbon - Hexoses

ketose

aldose

ketohexose

aldopentose

D-fructose

D-ribose

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The number of optical isomers: N=2n (number of asymmetric centers)
triose
tetroses
D-glyceraldehyde
D-eritrose
D-treose
Dexter-reference
compond

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Structure of monosaccharides.
Carbonyl and hydroxyl groups of monosaccharides react to form

intramolecular hemiacetal:

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The structure of monosaccharides is presented in three forms:
Fisher projection: straight

chain representation.
2. Haworth projection: simple ring in perspective.
3. Conformational representation: chair and boat configurations.

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Structure of monosaccharides.
β-Hemiacetal
hydroxyl
α-Hemiacetal
hydroxyl
Anomeric
center
Anomeric
center
D-Glucose
β,D-glucopyranose
α,D-glucopyranose
Dexter OH
Fisher projection

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Hydroxyl group at the anomeric center is called a hemiacetal or

glycoside. Diastereomers - stereoisomers that are not mirror images of each one. Anomers - diastereomers differing in configuration of the anomeric carbon atom. At the location of α-anomer hemiacetal hydroxyl is the same as "end" chiral center hydroxyl.

Characterisic tautomerism is ring-chain or cyclo-oxo tautomerism.

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α-Hemiacetal hydroxyl
Prospective Haworth formula (1929)

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Prospective Haworth formula
One can remember that the β anomer is

cis by the mnemonic,
"It's always better to βe up".

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Isomeric transformation of monosaccharides by the action of alkalis is called

epimerization.

Epimers are called diastereoisomers, that are differ by configuration of only one of several chiral centers (D-glucose and D-mannose, D-xylose and D-ribose, etc.).

Mutarotation is the change in specific rotation that occurs when an α or β form of a carbohydrate is converted to an equilibrium mixture of the two.

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Keto-endiol tautomerism
Epimerization in alkaline media

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1. Intermolecular dehydration
Chemical properties
Reaction to distinguish pentoses from hexoses.

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1. Intermolecular dehydration
Chemical properties
Reaction to distinguish pentoses from hexoses.

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Molish test
α-naphtol

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Selivanov’s test

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2. Reactions involving aldehyde group
Reaction with hydroxylamine
(the product with one less

carbon atom)

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Cyanohydrin’s synthesis
(the product with one more carbon atom)

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3. Reduction
diabetic
sweeteners

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4. a) Oxidation in neutral and mild acidic media
b) Oxidation
with

strong
oxidizers

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c) Oxidation by enzymes

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Identification of aldehyde group with:

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5. Glycosides formation:
Glycoside bonds
glycone
aglycone

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6. Acylation:
7. Alkylation:

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Disaccharides (bioses)
Depending on the method of the glycosidic bond formation
reducing

nonreducing

In reducing disaccharide glycoside bond is formed by hemiacetal (glycoside) hydroxyl group and one alcoholic hydroxyl group (usually at C4) of another monosaccharide.
Thus, there is one free hemiacetal hydroxyl group.

In nonreducing disaccharide there is absent free hemiacetal hydroxyl.

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Maltose

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Cellobiose

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Lactose

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Sucrose
"Inversion" - a sign change of the specific rotation after the

hydrolysis of sucrose.
A mixture of equal amounts of D-glucose and
D-fructose is invert sugar.

nonreducing
sugar

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Sucrose. chemical properties.
Doesn’t mutorotate
No silver mirror reaction
No reactions by aldehyde group
Hydrolysing

to glucose and fructose

Alkylation to ethers

Acylation to esters

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Amylose 20% Soluble in Н2О
Amylopectine 80%
Insoluble Н2О
Starch hydrolysis
Starch. Structure

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Amylose
α-1,4-glycosidic bond
Spiral structure

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Amylose with iodine forms clastrates of dark blue color.

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Amylopectin
α-1,6’-glycosidic bond
α-1,4’-glycosidic bond
branched structure

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Cellulose
Cellulose hydrolysis
β-1,4-glycosidic bond
linear structure

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Hyaluronic acid
β-1,3-glycosidic bond
β-1,4-glycosidic bond
D-glucuronic acid
D-N-acetylglucosamine
Heteropolysaccharides:

Слайд 39

Chondroitin sulfate
β-1,3-glycosidic bond
β-1,4-glycosidic bond
D-glucuronic acid
D-N-acetylgalactosamine

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Carbohydrates. mono-, di-, polysachcrides

Содержание

PLANClassification of carbohydrates.Nomenclature.Structural representations be Fisher and Haworth.Chirality. Optical isomers.Tautomerism. Mutarotation.Epimerization.Chemical

Carbohydrates The term "carbohydrate" was proposed by K.G. Shmidt in 1844.Cn(H2O)m

Carbohydrates. Classification. There are two classes of carbohydrates: simple carbohydrates and

Monosaccharide‘s classification. type of the carbonylgroupCarbon chain length3 Carbon - Trioses

The number of optical isomers: N=2n (number of asymmetric centers)triosetetrosesD-glyceraldehydeD-eritroseD-treoseDexter-reference compond

Structure of monosaccharides.Carbonyl and hydroxyl groups of monosaccharides react to form

The structure of monosaccharides is presented in three forms:Fisher projection: straight

Structure of monosaccharides.β-Hemiacetalhydroxylα-HemiacetalhydroxylAnomeric centerAnomeric centerD-Glucoseβ,D-glucopyranoseα,D-glucopyranoseDexter OHFisher projection

Hydroxyl group at the anomeric center is called a hemiacetal or

α-Hemiacetal hydroxylProspective Haworth formula (1929)

Prospective Haworth formula One can remember that the β anomer is

Isomeric transformation of monosaccharides by the action of alkalis is called

Keto-endiol tautomerism Epimerization in alkaline media

1. Intermolecular dehydrationChemical propertiesReaction to distinguish pentoses from hexoses.

1. Intermolecular dehydrationChemical propertiesReaction to distinguish pentoses from hexoses.

Molish testα-naphtol

Selivanov’s test

2. Reactions involving aldehyde groupReaction with hydroxylamine(the product with one less

Cyanohydrin’s synthesis (the product with one more carbon atom)

3. Reductiondiabeticsweeteners

4. a) Oxidation in neutral and mild acidic mediab) Oxidation with

c) Oxidation by enzymes

Identification of aldehyde group with:

5. Glycosides formation:Glycoside bondsglyconeaglycone

6. Acylation:7. Alkylation:

Disaccharides (bioses)Depending on the method of the glycosidic bond formation reducing

Maltose

Cellobiose

Lactose

Sucrose"Inversion" - a sign change of the specific rotation after the

Sucrose. chemical properties.Doesn’t mutorotateNo silver mirror reactionNo reactions by aldehyde groupHydrolysing

Amylose 20% Soluble in Н2ОAmylopectine 80%Insoluble Н2ОStarch hydrolysisStarch. Structure

Amyloseα-1,4-glycosidic bondSpiral structure

Amylose with iodine forms clastrates of dark blue color.

Amylopectinα-1,6’-glycosidic bondα-1,4’-glycosidic bondbranched structure

CelluloseCellulose hydrolysisβ-1,4-glycosidic bondlinear structure

Hyaluronic acidβ-1,3-glycosidic bondβ-1,4-glycosidic bondD-glucuronic acid D-N-acetylglucosamineHeteropolysaccharides:

Chondroitin sulfate β-1,3-glycosidic bondβ-1,4-glycosidic bondD-glucuronic acid D-N-acetylgalactosamine

HeparinL-iduronate-2-sulfateN-sulfo-D-glucosamine--6-sulfateα-1,4-glycosidic bond

Похожие презентации

PLAN
Classification of carbohydrates.
Nomenclature.
Structural representations be Fisher and Haworth.
Chirality. Optical isomers.
Tautomerism. Mutarotation.
Epimerization.
Chemical

Carbohydrates
The term "carbohydrate" was proposed by K.G. Shmidt in 1844.
Cn(H2O)m

Carbohydrates. Classification.
There are two classes of carbohydrates:
simple carbohydrates and

Monosaccharide‘s classification.
type of the carbonyl
group
Carbon chain length
3 Carbon - Trioses

The number of optical isomers: N=2n (number of asymmetric centers)
triose
tetroses
D-glyceraldehyde
D-eritrose
D-treose
Dexter-reference
compond

Structure of monosaccharides.
Carbonyl and hydroxyl groups of monosaccharides react to form

The structure of monosaccharides is presented in three forms:
Fisher projection: straight

Structure of monosaccharides.
β-Hemiacetal
hydroxyl
α-Hemiacetal
hydroxyl
Anomeric
center
Anomeric
center
D-Glucose
β,D-glucopyranose
α,D-glucopyranose
Dexter OH
Fisher projection

α-Hemiacetal hydroxyl
Prospective Haworth formula (1929)

Prospective Haworth formula
One can remember that the β anomer is

Keto-endiol tautomerism
Epimerization in alkaline media

1. Intermolecular dehydration
Chemical properties
Reaction to distinguish pentoses from hexoses.

1. Intermolecular dehydration
Chemical properties
Reaction to distinguish pentoses from hexoses.

Molish test
α-naphtol

2. Reactions involving aldehyde group
Reaction with hydroxylamine
(the product with one less

Cyanohydrin’s synthesis
(the product with one more carbon atom)

3. Reduction
diabetic
sweeteners

4. a) Oxidation in neutral and mild acidic media
b) Oxidation
with

5. Glycosides formation:
Glycoside bonds
glycone
aglycone

6. Acylation:
7. Alkylation:

Disaccharides (bioses)
Depending on the method of the glycosidic bond formation
reducing

Sucrose
"Inversion" - a sign change of the specific rotation after the

Sucrose. chemical properties.
Doesn’t mutorotate
No silver mirror reaction
No reactions by aldehyde group
Hydrolysing

Amylose 20% Soluble in Н2О
Amylopectine 80%
Insoluble Н2О
Starch hydrolysis
Starch. Structure

Amylose
α-1,4-glycosidic bond
Spiral structure

Amylopectin
α-1,6’-glycosidic bond
α-1,4’-glycosidic bond
branched structure

Cellulose
Cellulose hydrolysis
β-1,4-glycosidic bond
linear structure

Hyaluronic acid
β-1,3-glycosidic bond
β-1,4-glycosidic bond
D-glucuronic acid
D-N-acetylglucosamine
Heteropolysaccharides:

Chondroitin sulfate
β-1,3-glycosidic bond
β-1,4-glycosidic bond
D-glucuronic acid
D-N-acetylgalactosamine

Heparin
L-iduronate-2-sulfate
N-sulfo-D-glucosamine-
-6-sulfate
α-1,4-glycosidic bond