CARBOHYDRATES

Definition Polyhydroxy aldehyde, ketones and their derivatives. C6 (H2O)6, C12 (H2O)11, C18 (H2O)16

Functions Storage material for carbon and energy.

CONCEPTS OF ISOMERS

Two or more different compounds which contain the same number and types of atoms and the same molecular weights.

C6 (H2O)6,

C12 (H2O)11,

C18 (H2O)16

Projection formula: Spatial arrangement to represent 3-dimensional structure

CHO H C OH

CH2 OH
D-glyceraldehyde (Hydroxy group at the highest numbered asymmetric carbon atom is written to the right):

CHO HO C H CH 2 OH
L-glyceraldehyde (Hydroxy group at the highest numbered asymmetric carbon atom is written to the left): D-Erythrose is the mirror image of L-Erythrose.

Glyceraldehyde
Model Compounds of Monosaccharides D-Glyceraldehyde H O C H C OH L-Glyceraldehyde H C HO C H CH2 OH L-Threose
H C OH OH H HO C C OH H O

O

CH2 OH D-Erythrose
H C H H C C O

CH 2 OH

CH 2 OH

Mirror Image of Glucose
H C H HO H H C C C C O OH H OH OH O HO H HO HO H C C C C C H OH H H

CH2OH

CH2OH

D-glucose

L-glucose

Fisher Projection Form

H C

O

H C

OH

HO C

H

H C OH HO C H H C OH H C OH CH2 OH

H C OH HO C H H C OH H C CH2 OH O or

H C OH HO C H H C OH H C CH 2 OH O

Anomeric Carbon --- The carbon atom which is involved in hemiacetal or acetal formation.

Mirror Image of Glucose
H C H HO H H C C C C CH2OH OH H OH O O HO H HO OH HO H C C C C C H OH H H

CH2OH

E-D-glucose

E- L-glucose

Anomers
Stereoisomers formed when ring is formed (E, F).

H C

O

H C

OH

HO C

H

H C OH HO C H H C OH HO C H CH2 OH

H C OH O HO C H H C OH C H CH 2OH or O

H C OH HO C H H C OH C H

CH2 OH

E is same side with ring

Six and Five Member Rings

o

o

Pyran

Furan

Fisher & Harworth Projection Forms

H C

OH

6

H C OH HO C H H C OH H C CH2 OH O

CH2 OH O 5 1 2 OH OH

4 OH HO 3

E - D - Glucopyranose

E- and F- Glucose

E-Glucose

F-Glucose

H C H HO H H C C C C

OH

HO

H C

OH H OH O O

HO H HO

C C C C

H OH H H

CH2OH

CH2OH

E-D-glucose
CH2OH H H OH OH H OH O H OH H OH H OH H

E- L-glucose

O CH2OH H OH

OH

H H

MONOSACCHARIDES

1. Glucose

H C H C HO C

OH OH H OH O

6 CH2 OH 5 4 OH HO 3 O 1 2 OH OH

H C H C

CH 2 OH

E-D-Glucopyranose

Fisher Projection Form
H C H HO H H C C C C CH
2

OH OH H

H C O H HO H C C C C CH
2

OH OH H OH O

OH OH

H

OH

E -D-Glucofuranose0.5%) (
HO

H C H C C C C CH
2

O OH H OH OH OH

E -D-Glucopyranose (35%)

H H

Aldehydo-D-glucose (0.03%)

HO C H HO H H C C C C CH
2

H OH H

HO C O H HO H C C C C CH

H OH H OH O

OH OH

H

2

OH

F -D-Glucofuranose (0.5%)

F -D-Glucopyranose(65%)

2. Galactose
Component of lactose
CH2 OH O OH OH OH

HO

E-D-Galactopyranose

3.

Fructose

CH2 OH C O HO C H H C OH H C OH CH2 OH

CH2 OH HO C HO C H H C OH H C CH2 OH O or

CH2 OH OH C HO C H H C OH H C CH2 OH O

D-Fructose

F-D-Fructose

E-D-Fructose

Fructose
HOCH 2 O HO OH OH CH2 OH

HOCH 2

O HO

CH2 OH

OH OH

F - D - Fructofuranose
CH2 OH C O HO C H H C OH H C OH CH2 OH CH2 OH OH C HO C H H C OH H C H C H OH O

E - D - Fructofuranose

H O OH OH OH OH CH2OH

Naturally-occurring free form

Disaccharide
Anydrides of 2 monosaccharides

Linkage of Monosaccharides

Maltose
4-0-E-D-Glucopyranosyl- E-D-Glucopyranose

CH2 OH O HO OH O OH

CH2 OH O OH OH OH

Cellobiose
4-0-F-D-Glucopyranosyl -F-D-Glucopyranose

CH2 OH O HO OH OH O

CH2 OH O OH OH

OH

Sucrose
2-0-E-D-Glucopyranosyl F-D-Fructofuranoside
CH2 OH O HO OH O OH

1 CH2 OH O 2 3 OH HO 4

H 5 CH2 OH 6

Invert sugar is the hydrolyzed sucrose into glucose and fructose.

Lactose
Principal sugar in milk
CH2 OH OH O OH OH O CH2 OH O OH OH OH

4-0-F-D-Galactopyranosyl-E-D- Glucopyranose 4-0-F-D-Galactopyranosyl-F-D-Glucopyranose

Relative Sweetnes of Sugars
Sucrose Glucose Fructose Lactose Invert Sugar Maltose Galactose 100 74 174 16 126 32 32

Oligosaccharides

Raffinose
6-0-E-D-Galactopyranosyl-2-0-E-D-Glucopyranosyl -F-DFructofuranoside

2 2 2

2

el iose

ucrose

oiety

Stachyose
6-0-E-D-Galactopyranosyl-6-0-E-D-Galactopyranosyl -2-0-E-DGlucopyranosyl-F-D-Fructofuranoside ³Flatulence Factor´

2 2 2 2

2

Polysaccharides

Cellulose
Polymer of F-D-Glucose (1, 4) linkage. Repeating cellobiose moiety.

CH2 OH O OH OH OH O

CH2 OH O OH O

CH2 OH O OH

CH2 OH O

O

OH

OH

OH

OH

n

Cellulose

Starch
The reserve carbohydrate of plants. Occurs as granules in the cell. Made of amylose and amylopectin. Amylose --- Polymer of E-D- Glucose (1"4) linkage-straight-chain.

O O O O O O O

O O O O O

O O O

O O

O
O O

Amylose

Amylopectin
Polymer of E-D-Glucose (1->4) linkage in addition to E-D-Glucose (1"6) linkage.

The length of linear units in amylopectin is only 25. E-(1"4) linkage (25) to E-(1"6) linkage.

Amylose and Amylopectin

Glycogen
Animal starch. E - (1 " 4) linkage and E - (1 -> 6) linkage 12 : 1

Glycogen

Glycogen

Pectin
Polymer of 4-0-E-D-Galacturonic acid (1 4) & Methylgalacturonate

COOH
OH OH O O

COOCH 3
O OH O

COOCH 3
O OH

COOH
O

O

OH

OH

OH

OH

OH

Degree of Methylation (DM)

The higher the degree of methylation, the higher the temperature at which the gel forms.

For gel formation at least 50% of the carboxyl group are methylated. Pectin (about 74 DM) is used in jams. For jellies DM is about 60.

Functions of Carbohydrates

Functions of Polysaccharides

1. 2. 3. 4. 5.

Viscosity control Texture control Emulsifying agent Water-binding capacity Stabilizer

Corn Syrup
Enzyme H (
+

Corn Starch

Corn Syrup High Glucose Maltose Dextrose

Dextrose Equivalent (DE) =Gram of Reducing Sugar x 100 Gram of Total Sugar

The higher the DE, generally the greater the glucose content in corn syrup.

Amylose

High Fructose Syrups
Glucose in Syrup Glucose Isomerase Fructose

Generally: Glucose Fructose Maltose Isomaltose Higher Saccharides

50% 42% 1.5% 1.5% 5.0%

Corn Syrup
High Maltose Syrup Glucose Maltose Triose Tetrose Pentose 9 52 13 2 24 Low DE High DE
%

14 12 10 9 55

43 32 3 5 12

Modified Starches

Amylose

Modified Starches
1. Pregelatinized Starch --- Precooked and roll dried starch to give product that readily disperses in cold water.

2. Thin-boiling or Acid-modified Starch --- Suspended granular starch in a very dilute acid under somewhat below its gelatinization temperature (somewhat mild).

3. Oxidized Starches --- Oxidation of starch with alkaline hypochloride to get -COOH at C6.

Amylose

Carbohydrate Determination

Determination
1. Monosaccharides and Oligosaccharides A. Enzymatic Method 1. 2. B. 1. 2. 3. 2. Glucose oxidase Hexokinase Thin layer chromatography Gas chromatography Liquid column chromatography

Chromatography Method

Polysaccharides

E- and F- Glucose

Glucose Oxidase System
D-Glucose + O2
Glucose Oxidasse

Gluconic Acid + H2O2

H2O2+ 0 - Dianisidine (Colorless)

Peroxidase

2 H2O + Oxidized 0-Dianisidine (Brown)

H CO H2

OCH H2

H CO H

OCH H

Hexokinase System
Glucose + ATP G - 6 - P + NADP+
Hexokinase

G - 6 - P + ADP
+

G-6-P DH

Gluconate - 6 - phosphate + NADPH + H

G-6-P DH: Glucose-6-phosphate dehydrogenase NADP+ : NADPH : Nicotinamide Adenine Dinucleotide Phosphate Reduced Nicotinamide Adenine Dinucleotide Phosphate

The amount of NADPH formed in this reaction is stoichiometric with the amount of glucose. NADPH is measured by its absorption at 334 nm.

NAD
CONH2 O O P O CH2 N+ O

O

OH NH2 N N

OH

N N

-

O

P O

O

CH2 O

OH

OH

NADPH
H H

-O

O P O CH2 O

+ H+
N

OH O NH2 N N

OH

N N O

-O

P O

O

CH2

OH

OH

Qualitative Analysis
Thin Layer chromatography Silica gel as stationary phase Quantitation by densitomer

For Spot A Rf = A S

Solvent C B A A B S

Gas Chromatography
Requirement: Compounds must be volatile. Sugars form Trimethylsilyl Ether.

C Si C C

C Cl Si C C

Ether linkage

Trimethyl chlorosilane

Derivation of Glucose with Trimethylchlorosilane
6 CH2 OH O 5 4 OH HO 3 1 2 OH OH

CH 3 + 5Cl Si CH 3 Trimethylchlorosilane
6 CH2 O-Si(CH3)3 O 5 O-Si(CH ) 1
3 3

CH 3

Glucose

4 (CH3)3-Si-O

+

5HCl

3

2 O-Si(CH3)3 O-Si(CH3)3

Liquid Chromatography
Stationary Phase: Waters Associates. 840380 Solvent: H2O/CH3CN

Glucose

Fructose Maltose Maltotriose

Retention time

Polysaccharides
Quantification depends on chemical or enzymatic hydrolyses of them into monomers and analysis of the monomers. Qualitative Analyses 1. Amylose + IBlue color

Use spectrometer for determining the amylose - iodine blue color 2. Amylopectin + IReddish color.

Summary

Give a man a fish...

Teach a man to fish...

Stere c e istr :
e arra e e t f at s i - i e si al s ace. a sa t rself, ³cStere c e istr - e l r e las al as!´ ¶t es air!

The Agenda:
1. Define D & L; Alpha & Beta 2. Wake up whoever¶s asleep 3. Convert Fischer to Haworth 4. Wake up whoever¶s asleep 5. Follow the super-simple-steps super-simple6. HEY! WAKE UP! 7. Questions...

Fischer Projections of D & L Glucose
O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H H H HO H H H C C C C C C H D-Glucose O OH H OH OH OH

Check out the OHs on the last chiral carbon, that¶s how!
O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H H H HO H H H C C C C C C H D-Glucose O OH H OH OH OH

Oh, yeah, they¶re mirror images, too
Your basic mirror
O HO H HO HO HO C C C C C C H L-Glucose H H C C C C C C H D-Glucose O OH H OH OH OH

H H OH HO H H H H H H

Meet the Haworths...(Alpha and Beta)
H H C OH C H C HO OH C H H C OH H O H C OH H C HO OH C H H C OH H H C OH C H O OH C H

Alpha

Beta

What makes µem Alpha and Beta?
H H C OH C H C HO OH C H H C OH H O H C OH H C HO OH C H H C OH H H C OH C H O OH C H

Alpha = Trans

Beta = Cis

That¶s what makes µem Alpha and Beta!
H H C OH C C C C O C OH C C C H H C OH C H O OH C

Alpha = Trans

Beta = Cis

Fischer to Haworth...(Alpha-D Glucose) Haworth...(AlphaH H H HO H H H C C C C C C H O OH H OH OH OH H H HO H H H C C C C C C H OH OH H O OH OH H C OH C H C HO OH C H H C OH H O H C OH

Now! follow the supersupersimple six step process to figure out how to convert Fisher Projections to Haworth ring structures.

The Super-Simple Steps: Super1. Draw Fisher Projection (D form) 2. Flip D form if L is needed 2. Connect C1 with last chiral C 4. Draw Haworth w/ O on right 5. Attach Hydrogens, Hydroxyls, and Methanol Group 6. Alphabetize

Ready?

Here we go! Let¶s draw L-Glucose and convert that to Alpha-L, Alphashall we??

Step 1: The Fischer Projection in D Major
H H HO H H H C C C C C C H D-Glucose O OH H OH OH OH

Step 2: You¶ve got to Flip it! Flip it good!
O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H

Step 3: Connect the chiral with the carbonyl
HO HO O H HO HO C C C C C C H It¶s still L-Glucose, don¶t you know LH H OH H H H

Step 4: Draw the Haworth
Oxygen on the right, remember? C C C C O C

Has a nice ring to it, don¶t you think?

Step 5: Make attachments... based on Fischer Model
HO HO O H HO HO C C C C C C H H H OH H H H H C Right = Down Left = Up HO C H H C OH OH C H CH20H O

?
C

?

CH20H is down in L form

Step 6: Alpha-beta-ize (sorta) Alpha-betaBehold, Alpha-L-Glucose! H C HO C OH CH H H H C OH O OH C OH H C H

Note: CH20H points down in the L form

Sugar Stereo-Flow
Draw Fisher Projection (D-form)

art

Do you wanna end up with D or L??

I want D!

I want L!

Draw Basic Ring Structure (oxygen on right)

Flip D-form of Fisher Projection to make L form

Attach H and OH groups (use left/right rules)

Draw Basic Ring Structure (oxygen on right)

CH20H is UP! for D sugars

Attach H and OH groups (use left/right rules)

Do you want Alpha or Beta?

CH20H is DOWN! for D sugars

I want Beta!

I want Alpha!

Do you want Alpha or Beta?

CH2OH and anomeric OH are cis

CH2OH and anomeric OH are trans

I want Beta!

I want Alpha!

CH2OH and anomeric OH are cis

CH2OH and anomeric OH are trans

Steps 1 and 2: Flip the Fischer
H H HO H H H C C C C C C H D-Glucose O OH H OH OH OH O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H

Steps 3 & 5: Transfer Fischer Patterns to Haworth Model
O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H

?
C HO C H O

?
H C OH OH C H

?
C

?

Step 6: See to the anomeric carbon
O HO H HO HO HO C C C C C C H L-Glucose H H OH H H H H C HO C H H C OH CH20H O OH C OH H C H

Let¶s compare...
Alpha-L-Glucose H C HO C OH CH H H H C OH O OH C OH H C H H C HO OH C H H C OH H Alpha-D-Glucose H C OH C H O H C OH

Note: CH2OH and anomeric OH are trans to one another in the Alpha form

Can you dig it?

Sign up to vote on this title
UsefulNot useful