part 2: carbohydrateteppode/part12_carbohydrate...classification of carbohydrates mhidsils...

Part 2: CARBOHYDRATEPart 2: CARBOHYDRATE

SORACHAI SAELIM

DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOL1

The energy cycle of lifegy y

SORACHAI SAELIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOL2

Classification of Carbohydrates

M h id Si l S

Classification of Carbohydrates

• Monosaccharide or Simple Sugar• Complex CarbohydrateComplex Carbohydrate

– OligosaccharideP l h id– Polysaccharide


การเขยนสตรโครงสรางของนาตาลกลโคส

CHO1 2CH OHα-D-glucopyranoseสามารถเขยนได 3 แบบคอ

CHO

C OHH 2

3

2CH OH

HO5H H CH OH2

OC

C

HHO

OHH

3

4

H

HO

14 OH HOH H H

H

HO H

5

41

O

6

OHH

CH OH

C5 HO 23

OHH OH

H H

HOOH

H

3

2

1

CH OH2H

OH3

f tiHaworth projectionFischer conformationHaworth projection

projection

4

Monosaccharides• Monosaccharides are the simplest sugars, having the formula

(CH2O)n. The smallest molecules usually considered to be monosaccharides are triose with n = 3.

CHO CH2OH

OHH

HHO

O

HHO

H

HHO

H

Triose

• Monosaccharides can be categorized according to their value of 'n‘


•Monosaccharides can form five or six membered rings

d ll d f d ti land are called furanoses and pyranoses, respectively.

OHHOHH

HO

HH

O

FURAN

O CH2OHHOH2C

A FURANOSE

OH

HO H

OHOHO

OHHO

H

H

HH

H OH

O OHO

H

HCH2OH

HFuranose form

PYRAN

HO

A PYRANOSE


Classification of Monosaccharides1.Whether the sugar contains a ketone or an aldehyde group

2.The number of carbon atoms in the carbon chain

3. The stereochemical configuration of the asymmetric carbon g yatom farthest from the carbonyl group

OH

HO H

O

H

HOHO

HH

H OH

β-D-Glucofuranose


1.Whether the sugar contains a ketone or an aldehyde group

Trioses, the simplest

g p

Trioses, the simplest monosaccharides

aldehydes called aldosesaldehydes called aldoses

k t ll d k tketones called ketoses,



Triose 3 carbon

Tetrose 4 carbon

Pentose 5 carbon

Hexose 6 carbon

Heptose 7 carbon

CHO

OHH

CHO

OHH

CH2OH

OHHO

OHHHHO HHO

OHH

CH2OH

H

Triose

H

SORACHAI SAELIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOL

Hexose9

Classification of Monosaccharides

1.Whether the sugar contains a ketone or an aldehyde group

aldehydes called aldoses k t ll d k tketones called ketoses,


Triose 3 carbon

Tetrose 4 carbon

Pentose 5 carbonPentose 5 carbon

Hexose 6 carbon

Heptose 7 carbon

3. The stereochemical configuration of the asymmetric carbon atom farthest from the carbonyl group


D LD L

CHO CHO

CH2OH

H OH

CH OH

HO H

Fischer projectionC 2O CH2OH

ฟชเชอรโปรเจคชน หมายถงการเขยนรปโครงสราง 3 มตของสารอนทรยใหอยในรป 2 มต11

.......-Glucose D or L

CHO ..........-MannoseCHO

OHH CHO

.......... Mannose

HHOHHO

OHHHHO

OHHOHH

CH2OHHHO

CH2OHCH2OH


GlucoseAldose or ketose

.......-GlucoseM

CHO

CH2OH

..........-Mannose

OHH

HHO

CH2OH

OHHO

OHHHHO

OHH

OHH

HHO

CH2OHCH2OH


.............. จงอานชอของนาตาลชนดน

CHO........................

CHO

OHHCH2OH

HHOO

HHO

OHHOHH

OHH

CH2OH

HHO

CH OHCH2OH CH2OH


Stereochemical relationships of

the D- aldoses

15

Stereochemical relationships ofrelationships of the D-ketoses.

16

3. The stereochemical configuration of the asymmetric carbon atom farthest from the carbonyl groupcarbon atom farthest from the carbonyl group

การเขยนสตรโครงสรางของนาตาลกลโคส สามารถเขยนได 3 แบบคอ

CHO

C OHH

1

22CH OH CH OH2

OC

C

OHH

HHO

2

3

HO

14

5H HH H

H

HO H

5

4

O

OHH

C OH

C

H5

4

HO

1

23

4 OH HOH OH

H H

HOOH

HO H4

2

1

6

OHH

CH OH

C

2OHH H

OH3

conformationHaworth projection Fischer projection


Haworth projectionHaworth projectionCHO

C OHH

1

22CH OHC

C

OHH

HHO3

2CH OH

HO5H H

OHH

C OH

C

H5

4 H

HO

1

23

4 OH HOH

6

OHH

CH OH

C

2

HO 23

OHH

α-D-glucopyranose α-D-glucopyranose

Haworth projection

Fischer projectionFischer projection18

Formation of ring structures

19

3. The stereochemical configuration of the asymmetric carbon atom farthest from the carbonyl groupy g p


AAnomers

21

O O

OH H

H OH

β - anomer α- anomer


Mutarotation

HH 5 O

CH OH2 2CH OH

O5H OH

OHH

H

H

H

OH

OH

5

4

3 2

1

O

HO

H H

HO

O1

23

4

5

OH

OH

H

HH

OH

2CH OHH

β-D-glucopyranose -D-glucopyranoseα36 % 63 %

H

HOC

OH O

H123

4

5

OH

OH

H

H

H

OHH

OCH

HO

CH OH2

OH H H OHHOH2CH OH

OCH

HO

D-glucose< 0.1 %

HO

HOHH

OH HH OH

H

HO

α β-D-glucofuranose -D-glucofuranose

1 %

α βD glucofuranose


OHO

H

HO

HO H

OHOHO

HH

H OH

β D Glucofuranoseβ-D-Glucofuranose


D-GlucoseDrawing cyclic structure

D-Glucose

CHO1

Case 1. Six membered ring

OHH

HHO

2

3

1. Lay down the Fischer projection:

right = down, left=upHHO

OHH2. Rotate the C5 bond to put the –OH in

OHH

CH2OH

place (For a D sugar, the –CH2OH goes up.)


D-Glucose3. Close the ring, (-OH to CHO)

CHO

OHH

HHO

3. Close the ring, ( OH to CHO)

β anomer OH up HHO

OHH

OHH

β - anomer -OH up

α- anomer -OH down CH2OH

α anomer OH down


D-GlucoseDrawing cyclic structure

D-Glucose

CH2OH 1 L d th Fi h j ti

Case 2. Five membered ring 2

O

HHO

1. Lay down the Fischer projection:

right = down, left=upHHO

OHH2. Rotate the C5 bond to put the –OH in place

OHH

CH2OH

(For a D sugar, the –CH2OH goes up.)


3. Close the ring, (-OH to CHO)

β - anomer -OH up D-Glucose

α- anomer -OH down CH2OH

O

1

2

HHO

OHH OHH

OHH

CH OHCH2OH


Drawing cyclic structureEX EX 11..

D-Galactose

Drawing cyclic structure

CHO

OHH

HHO

HHO

OHH

CH2OH


Drawing cyclic structureEX EX 22..

......................g y

CH2OH

O ป O

OHH

1. ปดวง 5 เหลยม

2 ป 6 OHH

OHH


CH2OH


Test Drawing cyclic structureCHO

D

Test Drawing cyclic structure

HHO

HHO

D-Mannose

OHH

1 ปดวง 5 เหลยมOHH

CH2OH


2 ปดวง 6 เหลยมCH2OH 2. ปดวง 6 เหลยม

31

Reaction of sugarg

• Sugar + methanol/HCl methyl acetals

(glucoside, mannosides, fructosides etc.)(g ucos de, a os des, uc os des e c )

32

CH3OH, HClO

H

HOH

OH

O

H

HOH

OH

O

HH

OH

H

HOOHH

HO

H

HO

OCH3

OHHH

OHO

H

HO

H

HOHH

OCH3OH

M h iMechanism

33

Hydrolysis:

34

Enolization, Tautomerization และ Isomerization

• monosacharides ละลายในเบสจะเกด enolization และ keto-enol

tautomerization และนาไปสการเกด isomerization

CHO CHO C CHOO-H

OHHHHOOHHOHH

C OHHHOOHHOHH

CC OH

HHOOHHOHH

CHOHOHHHOOHHOHH

OH-

OH-

H2O

H2O

CH2OH CH2OH CH2OHOHH

CH2OH

D-glucose D-MannoseEnolate ion

H2O OH-

COHHCH2OH

Lobry de Bruyn-Alberda

van EkensteinC OH

HHOOHHOHH

C OHHOOHHOHH

Tautomerization

transformation

35CH2OHCH2OH

D-Fructose Enediol

ป pentamethyl deirvetive ทาปฏกรยากบกรดจะสามารถ

ทาปฏกรยากบ –OCH3 เฉพาะตาแหนงแอลฟาคารบอน

36เทานน

tert-butyldiphenylsilyl (TBDPS) จะสามารถเกดปฏกรยาy p y y ( ) ฏ

เฉพาะ primary hydroxyl group

37

Ester formationEster formation

monosaccharide เมอทาปฏกรยากบ acetic anhydride ใน เบสออน จะmonosaccharide เมอทาปฏกรยากบ acetic anhydride ใน เบสออน จะ

สามารถเกดปฏกรยากบหม –OH ในวงนาตาลเกดเปน ester

38

Cyclic acetalsy

39

ปฏกรยา Oxidation ของ Monosacharideปฏกรยา Oxidation ของ Monosacharide

ใ • Tollens test (Silver mirror test) ใชทดสอบนาตาลรดวซ (reducing sugar) ซง

จะใหผล positive กบนาตาล aldoses และ ketose

สารละลาย Benedict เปนสารละลายททาหนาทตรวจสอบนาตาลรดวซเชน

เดยวกบ Tollens ทสามารถทาสอบนาตาลรดวซได ซงนาตาล

รดวซจะเปลยนสารละลาย Benedict จากสนาเงนเปนสแดง โดยปฏกรยาท

เกดขนเกดจาก Cu2+ ไปเปน Cu+

40

Reducing sugarg g

41

Reducing sugar

CH2OH CH2OH CH2OH CH2OH H

g g

OH

OH

H

H

O

OHH

OH OH

HH

OHH

OHH

O

OH

OHH

OHH

OHH

HCH2OH

CH2OH

H

OH

O

HO

OHH OHHMaltose

O OHCH2OH

OHHHOH

Sucrose

OOHHOH

CH2OH

H

OH OH

HH

OHH

OHH

O

HOHH

OHHH

Lactose

42

ปฏกรยา Oxidation ของ Monosacharideปฏกรยา Oxidation ของ Monosacharide

• Bromine water: การสงเคราะห aldonic acid เกด oxidizes –CHO

ใหกลายเปน -CO2H2

Nitric Acid Oxidation: Nitric acid เปน strong oxidizing

agent มากวา bromine ในนา โดยจะ oxidize ทง –CHO และ

–CH2OH ของ aldose ไปเปน –COOH 2

3

2

44

ปฏกรยา Oxidation ของ Monosacharideฏ O dat o ง o osac a de

Periodate Oxidations: Oxidative Cleavage ของ Polyhydroxy compounds

To provide the structure of an unknown

carbohydrate.

Also, the size of the carbohydrate can be , y

revealed by the amount of periodic acid that

is consumed.

One equivalent of periodic acid corresponds

To provide clues as to whether the carbohydrate in

question is an aldose or a ketose.

Oxidize CO One equivalent of periodic acid corresponds

to one carbon-carbon bond cleavage.

Ex. a six-carbon carbohydrate would

f

Oxidize CO2

consume 5 equivalents of periodic acid.

45

MechanismMechanism

46

ปฏกรยา Oxidation ของ Monosacharide

Example

47

D-glucose into five equivalents of formic acid and one

equivalent of formaldehyde.equivalent of formaldehyde.

48

22

2

D-fructose to three equivalents of formic acid, two equivalents

of formaldehyde and one equivalent of carbon dioxideof formaldehyde, and one equivalent of carbon dioxide.

49

Red ction ของ Monosacharide

Ald K t ซโ N BH

Reduction ของ Monosacharide

• Aldose และ Ketose สามารถถกรดวซโดย NaBH4 เกด

สารประกอบ alditols

50

Kiliani-Fischer Synthesis

• วธการเตมคารบอนลงในสายโซของ monosaccharide

51

The Ruff degradationThe Ruff degradation

52

Oligosaccharides

• Glycosidic bonds between monosaccharides give rise to oligosaccharides and polysaccharidesoligosaccharides and polysaccharides.

• The simplest oligosaccharides, the disaccharides, include compounds such as sucrose and lactose which are referred to as sugars (like thesuch as sucrose and lactose, which are referred to as sugars (like the monosaccharides).

O HCH2OH

O HCH2OH

OH

OH

H

OHH

OHH

OHH

OH

OH

H

OHH

OHH

OHH

OHH OHH

O HCH2OH

O HCH2OH

OH

OH

H

H

OHH

OHH

OH H

OHH

OHH

OHH

O

H2O

SORACHAI SAELIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOLSORACHAI SAELIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOL53

OHH OHH

Formation of lactoseFormation of lactose

SORACHAI SAELIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITTAYANUSORN SCHOOL

54

PolysaccharidesPolysaccharides

• Polysaccharides are polymers of monosaccharide units.

• Polysaccharides are used to some extent for energy storage in almost all higher organisms.

• Animals use glycogen. Pl t t h hi h i d f l d l ti I• Plants use starch, which is composed of amylose and amylopectin. In both plants and animals, the polysaccharides used for energy storage are readily broken down into monomeric units that can be rapilymetabolized to produce ATP. In addition to polysaccharides used for energy storage, plants use different polysaccharides, such as cellulose, for structural purposes in their cell walls. The exoskeleton of many arthropods and mollusks is composed of chitin, a polysaccharide of N-acetyl-D-glucosamine.p y y g

58

Polysaccharidesy


Common polymers, their monomeric units, and linkages/branches are shown

below:

Polysaccharide Monomeric Unit LinkagesPolysaccharide Monomeric Unit LinkagesName

Gl D Gl 1 6 b hGlycogen D-Glucose 1->6 branchesCellulose D-Glucose 1->4Chitin N-Acetyl-D-glucosamine 1->4y gAmylopectin D-Glucose 1->6 branchesAmylose D-Glucose 1->4

60

StarchStarch


AmyloseAmylose

CH2OH CH2OH CH OH CH OH CH OHO

CH2OH

O

OCH2OH

O

OCH2OH

O

OCH2OH

O

OCH2OH

O


Amylopectiny p


CellulosesCellulosesCH OH

OCH2OH

OHOH

OCH2OH

OCH OHOH

OOH

OH

OO

CH2OH

OHO

OCH2OH

OH OCH OHOH

OH

OHO

CH2OH

OHO

O

OOH


สวนประกอบหลกของแปงสวนประกอบหลกของแปง


สวนประกอบหลกของเซลลโลสและไกลโคเจน


part 2: carbohydrateteppode/part12_carbohydrate...classification of carbohydrates mhidsils...

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