carbohydrates chemistry 1

8/8/2019 Carbohydrates Chemistry 1

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CARBOHYDRATES


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Definition

Polyhydroxy aldehyde, ketones and their derivatives.

C6

(H2

O)6,

C12

(H2

O)11,

C18

(H2

O)16

Functions

Storage material for carbon and energy.


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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


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D-glyceraldehyde (Hydroxy group at the highest numbered asymmetric

carbon atom is written to the right):

CH2OH

CHO

C HHO

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.

CH2OH

OH

CHO

CH


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Glyceraldehyde

Model Compounds of Monosaccharides

C

O

CH2OH

OHCH HO HC

CH2OH

H H O

C

CO

CH2

OH

OHCH

HO H

C

CH 2 OH

H H OC

H C OH

OH

C

H

D-Glyceraldehyde L-Glyceraldehyde

D-Erythrose L-Threose


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Mirror Image of GlucoseMirror Image of Glucose

C O

H

C OHH

CHO H

C OHH

C OHH

CH2OH

CO

H

CHO H

C OHH

CHO H

CHO H

CH2OH

D-glucose L-glucose


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Fisher Projection Form

CO

CH2OH

OHCH

HO

H

HC

OH

OH

CH

HO

H C OH

OH

CH

H C OH

C H

H

HO

H C

CH2OH

O

C C

O

CH2OH

CH

HO

H

HC

OHCH

H C

OH

or

Anomeric Carbon --- The carbon atom which is involved in

hemiacetal or acetal formation.


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Mirror Image of GlucoseMirror Image of Glucose

E-D-glucose E- L-glucose

C

H

C OHH

CHO H

C OHH

CH

CH2OH

O

OH

C

H

CHO H

C OHH

CHO H

C H

CH2OH

O

HO


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Anomers

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

C

O

CH2OH

OHCH

HO

H

HC

OH

OH

CH

HO

HO HC

OH

C H

H C OH

C H

H

HO

H C

CH2OH

O

C C

O

CH2OH

CH

HO

H

HC

OHCH

HC

OH

or

E is same side with ring


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Six and Five Member RingsSix and Five Member Rings

PyranFuran

o o


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Fisher & Harworth Projection Forms

OH

OH

CH

H C OH

C H

H

HO

H C

CH2OH

O

C

OH

O

OH

OHHO

CH2OH

1

23

45

6

E - D - Glucopyranose


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EE-- andand FF-- GlucoseGlucose


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EE--GlucoseGlucose FF--GlucoseGlucose


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O

OH

OH

OH

OH

CH2OH

H

H

H

HH

O

H

H

H

H

H

OH

OH

OH

OHCH2OH

C

H

C OHH

CHO H

C OHH

CH

CH2OH

O

OH

C

H

CHO H

C OHH

CHO H

C H

CH2OH

O

HO

E-D-glucose E- L-glucose


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MONOSACCHARIDES


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1. Glucose

OH

OH

CH

H C OH

C H

H

HO

H C

CH2OH

O

C

OH

O

OH

OHHO

CH2OH

1

23

4

5

6

E-D-Glucopyranose


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HOC

O

CH 2 OH

CH

HO

H

HC

OHCH

H C

OH

HO

OH

CH

H C

OH

C H

H

HO

H C

CH 2 OH

O

C

C

O

CH 2 OH

CH

HO

H

HC

OH

CH

H C

OH

OH

CO

CH 2 OH

OHCH

HO

H

HC

OHCH

OHH C

OH

OH

CH

H C OH

C H

H

HO

H C

CH 2 OH

O

C

-D-Glucofuranose(0.5%)E E-D-Glucopyranose(35%)

-D-Glucofuranose

(0.5%)

F F -D-Glucopyranose(65%)

Aldehydo-D-glucose(0.03%)

Fisher Projection Form


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2. Galactose

Component of lactose

E-D-Galactopyranose

O

OH

OH

CH2OH

HO

OH


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3. Fructose

D-Fructose F-D-Fructose E-D-Fructose

CH2OH

O

CH2OH

CHO HC

OHCH

H C

OH

O

CH2OH

CHO HC

OHCH

H C

CH2OHCH2OH

CH

HO

H C OH

C HHO

C

OH

CH2OH

O

or


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F - D - Fructofuranose E - D - Fructofuranose

O

HO

OH

CH2OH

HOCH2 OH O

HO

OH

HOCH2 CH2OH

OH

O

OH

CH2OH

H

OH

OH

OH

CH2OH

C

HO HC

OHCH

H C

OH

O

OH

CH2OH

CH

H C OH

C H

H

HO

H

C

OH

CH2OH

O

C

Naturally-occurring free form

Fructose


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DisaccharideDisaccharide

Anydrides of 2 monosaccharides


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Linkage of MonosaccharidesLinkage of Monosaccharides


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

O

OH

OHHO

CH2OH

O

OH

OH

CH2OH

OOH

Maltose


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O

OH

OH

HO

CH2OH

O

OH

OH

CH2OH

O

OH

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

Cellobiose


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2-0-E-D-GlucopyranosylF-D-Fructofuranoside

O

OH

OHHO

CH2OH

CH2OH

OCH2OH

O

HO

OH

H

1

2

3 4

5

6

Invert sugar is the hydrolyzed sucrose into glucose and fructose.

Sucrose


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Relative Sweetnes of Sugars

Sucrose 100

Glucose 74

Fructose 174

Lactose 16

Invert Sugar 126

Maltose 32

Galactose 32


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OligosaccharidesOligosaccharides


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6-0-E-D-Galactopyranosyl-2-0-E-D-Glucopyranosyl -F-D-Fructofuranoside

2

2

2

2

el ioseucrose oiety

Raffinose


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6-0-E-D-Galactopyranosyl-6-0-E-D-Galactopyranosyl -2-0-E-D-

Glucopyranosyl-F-D-Fructofuranoside

Flatulence Factor

2

2

2

2

2

Stachyose


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PolysaccharidesPolysaccharides


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Polymer ofF-D-Glucose (1, 4) linkage.

Repeating cellobiose moiety.

O

OH

OH

CH2OH

OH

O OO

O

OH

OH

CH2OH

O

OH

OH

CH2OH

O

OH

OH

CH2OH

O

OH

OH

CH2OH

O

OH

OH

CH2OH

O

OH

OH

CH2OH

O

OH

OH

CH2OH

n

Cellulose


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CelluloseCellulose


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The reserve carbohydrate of plants. Occurs as granules in the cell.

Made of amylose and amylopectin.

Amylose --- Polymer ofE-D- Glucose (1"4) linkage-straight-chain.

Starch

O

O

O

O

OO OO

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O


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Amylose


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Amylopectin

Polymer ofE-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.


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Amylose and AmylopectinAmylose and Amylopectin


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Glycogen

Animal starch.

E - (1 " 4) linkage and E - (1 -> 6) linkage12 : 1


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Glycogen


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Polymer of4-0-E-D-Galacturonic acid (1 4) &

Methylgalacturonate

Pectin

O

OH

OH

OH

O OO

O

OH

OH

O

OH

OH

O

OH

OH

O

OH

OH

O

OH

OH

COOH COOCH 3 COOCH 3 COOH


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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.


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Functions of Carbohydrates


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Corn Syrup

Corn StarchEnzyme

H

(

Corn Syrup

High Glucose

Maltose

Dextrose

+

Dextrose Equivalent (

DE) =

Gram of Reducing Sugar

Gram of Total Sugar x 100

The higher the DE, generally the greater the glucose

content in corn syrup.


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AmyloseAmylose


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High Fructose Syrups

Generally: Glucose 50%

Fructose 42%

Maltose 1.5%Isomaltose 1.5%

Higher Saccharides 5.0%

Glucose in Syrup FructoseGlucose Isomerase


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Corn Syrup

%

Glucose 9 14 43

Maltose 52 12 32

Triose 13 10 3

Tetrose 2 9 5

High Maltose Syrup Low DE High DE

Pentose 24 55 12


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Modified Starches


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Amylose


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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.

Modified Starches


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Amylose


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Carbohydrate Determination


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1. Monosaccharides and Oligosaccharides

A. Enzymatic Method

1. Glucose oxidase

2. Hexokinase

B. Chromatography Method

1. Thin layer chromatography

2. Gas chromatography3. Liquid column chromatography

2. Polysaccharides

Determination


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Glucose Oxidase System

D-Glucose + O2 Gluconic Acid + H2O2

H2O2+ 0 - Dianisidine 2 H2O + Oxidized 0-Dianisidine

(Colorless) (Brown)

OCHH CO

H2 H2

H CO OCH

H H

Glucose Oxidasse

Peroxidase


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Hexokinase System

The amount of NADPH formed in this reaction is stoichiometric with theamount of glucose.

NADPH is measured by its absorption at 334 nm.

Glucose + ATP G - 6 - P + ADP

G - 6 - P + NADP+ Gluconate - 6 - phosphate + NADPH + H+

Hexokinase

G-6-P DH

NADP+ : Nicotinamide Adenine Dinucleotide Phosphate

NADPH : Reduced Nicotinamide Adenine Dinucleotide Phosphate

G-6-P DH: Glucose-6-phosphate dehydrogenase

NAD


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NAD

P

O

OO

O

P

O

OO CH2

CH2

O

OH OH

N

N N

N

NH2

O

OH OH

N

CONH2

-

-

+


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NADPH

P

O

OO

O

P

O

OO CH2

CH2

O

OH OH

N

N N

N

NH2

O

OH OH

-

-

N

H H

+ H+


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Qualitative Analysis

Thin Layer chromatography

Silica gel as stationary phase

Quantitation by densitomer

A

BC

A B

S

Solvent

Rf =A

S

For SpotA


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Requirement: Compounds must be volatile.

Sugars form Trimethylsilyl Ether.

Si SiCl

C

C

C

C

C

C

Ether linkage Trimethyl chlorosilane

Gas Chromatography


62/94

OH

O

OH

OHHO

CH2OH

1

23

45

6

+ Si

CH3

CH3

CH35Cl

O-Si(CH3)3

O

O-Si(CH3)3

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

CH2O-Si(CH3)3

1

23

45

6

5HCl+

Derivation ofGlucose with Trimethylchlorosilane

Glucose Trimethylchlorosilane


63/94

Liquid Chromatography

Fructose

Glucose

Maltotriose

Maltose

Stationary Phase: Waters Associates. 840380

Solvent: H2O/CH3CN


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Polysaccharides

Quantification depends on chemical or enzymatic hydrolyses ofthem into monomers and analysis of the monomers.

Qualitative Analyses

1. Amylose + I- Blue color

Use spectrometer for determining the amylose - iodine blue color

2. Amylopectin + I- Reddish color.


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SummarySummary


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67/94

Give a man a fish...

Teach a man to fish...


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69/94


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71/94

1. Define D & L; Alpha & Beta1. Define D & L; Alpha & Beta

2. Wake up whoevers asleep2. Wake up whoevers asleep

3. Convert Fischer to Haworth3. Convert Fischer to Haworth4. Wake up whoevers asleep4. Wake up whoevers asleep

5. Follow the super5. Follow the super--simplesimple--stepssteps

6. HEY! WAKE UP!6. HEY! WAKE UP!

7. Questions...7. Questions...

The Agenda:The Agenda:


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C

C

C

C

C

C

OH

H

H

H

H

H

H

H

O

OH

OH

OH

HO

DD--GlucoseGlucoseDD--GlucoseGlucose

Fischer Projections of D & L GlucoseFischer Projections of D & L GlucoseFischer Projections of D & L GlucoseFischer Projections of D & L Glucose

LL--GlucoseGlucoseLL--GlucoseGlucose

C

C

C

C

C

C

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH


73/94

C

C

C

C

C

C

OH

H

H

H

H

H

H

H

O

OH

OH

OH

HO

LL--GlucoseGlucoseLL--GlucoseGlucose DD--GlucoseGlucoseDD--GlucoseGlucose

C

C

C

C

C

C

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH

Check out the OHs on the lastCheck out the OHs on the last

chiral carbon, thats how!chiral carbon, thats how!

Check out the OHs on the lastCheck out the OHs on the last

chiral carbon, thats how!chiral carbon, thats how!


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Oh, yeah, theyre mirror images, tooOh, yeah, theyre mirror images, tooOh, yeah, theyre mirror images, tooOh, yeah, theyre mirror images, too

C

C

C

C

C

C

OH

H

H

H

H

H

H

H

O

OH

OH

OH

HO

DD--GlucoseGlucoseDD--GlucoseGlucoseLL--GlucoseGlucoseLL--GlucoseGlucose

C

C

C

C

C

C

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH

Your basic

mirror

Your basic

mirror


75/94

Meet the Haworths...(Alpha and Beta)Meet the Haworths...(Alpha and Beta)Meet the Haworths...(Alpha and Beta)Meet the Haworths...(Alpha and Beta)

H

OC

C C

CC

OH

HO OH

OH

OH

CH

HH

H

H

H

H

OC

C C

CC

OH

HO OH

OH

OH

CH

HH

H

HH

AlphaAlpha BetaBeta


76/94

What makes em Alpha and Beta?What makes em Alpha and Beta?What makes em Alpha and Beta?What makes em Alpha and Beta?

H

OC

C C

CC

OH

HO OH

OH

OH

CH

HH

H

H

H

H

OC

C C

CC

OH

HO OH

OH

OH

CH

HH

H

HH

Alpha = TransAlpha = Trans Beta = CisBeta = Cis


77/94

Thats what makes em Alpha and Beta!Thats what makes em Alpha and Beta!Thats what makes em Alpha and Beta!Thats what makes em Alpha and Beta!

H

OC

C C

CC

OH

OH

CH

H

OC

C C

CC

OH

OH

CH

H

Alpha = TransAlpha = Trans Beta = CisBeta = Cis


78/94

Fischer to Haworth...(AlphaFischer to Haworth...(Alpha--D Glucose)D Glucose)Fischer to Haworth...(AlphaFischer to Haworth...(Alpha--D Glucose)D Glucose)

C

C

C

C

C

C

OH

H

H

H

H

H

H

H

O

OH

OH

OH

HO

C

C

C

C

C

C

OH

H

H

H

H

H

H

H

OH

OH

OH

OHO

OC

C C

CC

HO OH

OH

OH

OHCH

H

HH

H

H

H


79/94

Now!Now!

follow the superfollow the super--

simplesimple sixsix stepstep

process to figure out how toprocess to figure out how to

convert Fisher Projections toconvert Fisher Projections to

Haworth ring structures.Haworth ring structures.


80/94

1. Draw Fisher Projection (D form)1. Draw Fisher Projection (D form)

2. Flip D form if L is needed2. Flip D form if L is needed

2. Connect C1 with last chiral C2. Connect C1 with last chiral C

4. Draw Haworth w/ O on right4. Draw Haworth w/ O on right

5. Attach Hydrogens, Hydroxyls,5. Attach Hydrogens, Hydroxyls,and Methanol Groupand Methanol Group

6. Alphabetize6. Alphabetize

The SuperThe Super--Simple Steps:Simple Steps:The SuperThe Super--Simple Steps:Simple Steps:


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Ready?Ready?


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Here we go!Here we go!

Lets drawLets draw LL--GlucoseGlucose

and convert that toand convert that to AlphaAlpha--LL,,

shall we??shall we??


83/94

Step 1: The Fischer ProjectionStep 1: The Fischer Projection

in D Majorin D MajorC

C

C

C

CC

OH

H

H

H

H

H

H

H

O

OH

OH

OH

HO

DD--GlucoseGlucoseDD--GlucoseGlucose


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Step 2: Youve got to Flip it!Step 2: Youve got to Flip it!

Flip it good!Flip it good!


C

C

C

C

C

C

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH


85/94

Step 3: Connect the chiralStep 3: Connect the chiral

with the carbonylwith the carbonyl

C

C

C

C

C

C

HO

H

H

H

H

H

H

H

HO

HO

HO

O OH

Its still LIts still L--Glucose, dont you knowGlucose, dont you knowIts still LIts still L--Glucose, dont you knowGlucose, dont you know


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Step 4: Draw the HaworthStep 4: Draw the Haworth

Has a nice ring to it, dont you think?Has a nice ring to it, dont you think?Has a nice ring to it, dont you think?Has a nice ring to it, dont you think?

OC

C C

CC

Oxygen on the right,remember?


87/94

Step 5: Make attachments...Step 5: Make attachments...

based on Fischer Modelbased on Fischer Model

C

C

C

C

C

C

HO

H

H

H

H

H

H

H

HO

HO

HO

O OH Right = Down

Left = Up

OC

C C

CC

HO

OH

OHH H

?

H

?

CH20H

H

CH20H is down in L formCH20H is down in L form


88/94

SugarStereo-Flow art


89/94

g

CH2OH and anomeric OH

are cis

I want Beta!


are trans

I want Alpha!

Do you want Alpha or Beta?

CH20H is UP! for D sugars

Attach H and OH groups

(use left/right rules)

Draw Basic Ring Structure

(oxygen on right)

I want D!


are cis

I want Beta!


are trans

I want Alpha!

Do you want Alpha or Beta?

CH20H is DOWN! for D sugars

Attach H and OH groups

(use left/right rules)

Draw Basic Ring Structure

(oxygen on right)

Flip D-form of Fisher Projection

to make L form

I want L!

Do you wanna end up with D or L??

Draw Fisher Projection

(D-form)


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91/94

Steps 3 & 5: Transfer Fischer PatternsSteps 3 & 5: Transfer Fischer Patterns

to Haworth Modelto Haworth Model


C

C

C

C

CC

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH

OC

C C

CC

HO

OH

OHH H

?

H

?

?

?


92/94

Step 6: See to the anomeric carbonStep 6: See to the anomeric carbon


C

C

C

C

CC

HO

H

H

H

H

H

H

H

O

HO

HO

HO

OH

OC

C C

CC

HO

OH

OHH H

H

H

CH20H OH

H


93/94

Lets compare...Lets compare...

OC

C C

CC

HO

OH

OHH H

H

C OHH H

H

OH

H

Alpha-L-Glucose

Note: CH2OH and anomeric OH are

trans to one another in the Alpha form

OC

C C

CC

HO OH

OH

OH

OHCH

H

HH

H

H

H

Alpha-D-Glucose


94/94

Can you dig it?Can you dig it?

carbohydrates chemistry 1

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