Carbohydrates

Chapter 25

25-1

Carbohydrates
x

Carbohydrate: A polyhydroxyaldehyde, a polyhydroxyketone, or a compound that gives either of these compounds after hydrolysis. Monosaccharide: A carbohydrate that cannot be hydrolyzed to a simpler carbohydrate.
They have the general formula CnH2nOn, where n varies from 3 to 8. Aldose: a monosaccharide containing an aldehyde group. Ketose: a monosaccharide containing a ketone group.

25-2

Importance of Carbohydrates to us.

polymerize CO2 + H2 O photosynthesis glucose chlorophyll light polymerize

cellulose giving structure to plants

clothing fiber wood

starch, plant seeds eaten by animals

CO2 + H2 O + energy

glucose

glycogen (liver)

25-3

Monosaccharides
x

Monosaccharides are classified by their number of carbon atoms:

Name Triose Tetrose Pentose Hexose Heptose Octose Formula C2H2 2 O C2H2 2 O C2H2 O2 2 C2H2 O2 2 C2H2 O2 2 C2H2 O2 2

25-4

Monosaccharides
x

There are only two trioses:

CHO CHOH CH2OH Glyceraldehyde (analdotriose) CH2OH C=O CH2OH Dihydroxyacetone (aketotriose)

Chiral Center R and S stereoisomers

These compounds are referred to simply as trioses, tetroses, and so forth tellling the number of carbon atoms present.

25-5

Review Fischer Projections

x

Fischer projection: A two dimensional representation for showing the configuration of carbohydrates.
Horizontal lines represent bonds projecting forward. Vertical lines represent bonds projecting to the rear. The more highly oxidized carbon is shown at the top.

CHO H C OH

converttoa Fischerprojection

CHO H
.

OH

CH2OH (R)Glyceraldehyde (threedimensional representation)

CH2OH (R)Glyceraldehyde (Fischerprojection)

25-6

D,L Monosaccharides
x

In 1891, Emil Fischer made the arbitrary assignments of D- and L- to the enantiomers of glyceraldehyde.
CHO H OH CH2OH CHO HO H CH2OH

DGlyceraldehyde LGlyceraldehyde (R)Glyceraldehyde (S)Glyceraldehyde 2 2 []2 =+ 22 .2 []2 =22 .2

D D

25-7

D,L Monosaccharides
x

According to the conventions proposed by Fischer:

D-monosaccharide: A monosaccharide that has the same configuration at its penultimate (next to bottom) carbon as D-glyceraldehyde; that is, its -OH is on the right when written as a Fischer projection. L-monosaccharide: A monosaccharide that has the same configuration at its penultimate carbon as Lglyceraldehyde; that is, its -OH is on the left when written as a Fischer projection.

25-8

D,L Monosaccharides
x

D-aldotetroses and the two most abundant Daldopentoses in the biological world:
CHO CHO H OH H OH DErythrose CH2OH CHO HO H H OH DThreose CH2OH H H H OH OH OH CH2OH DRibose H H H CHO H OH OH CH2OH 2 DeoxyD ribose

D-aldotetroses Expect four stereoisomer 22 for aldotetroses. Two D and two L.

D-aldopentoses Expect total of 8 (=23) steroisomers. Four D, four 25-9 L.

D,L Monosaccharides
x

The most abundant hexoses:

CHO H OH HO H H OH H OH CH2OH D-Glucose CHO H OH HO H HO H H OH CH2 OH D-Galactose CH2OH C O HO H H OH H OH CH2OH D-Fructose

aldohexoses Expect 16 stereoisomers 24 for aldohexoses. Eight D and eight L.

ketohexose Expect 8 stereoisomers 24 for ketohexoses. Four D and four L.

25-10

D Aldohexoses binary display

DAllose
CHO

DAltrose
CHO OH OH OH OH HO H H H H OH OH OH CH2 OH H HO H H

DGlucose
CHO OH H OH OH CH2 OH HO HO H H

DMannose
CHO H H OH

All altruists gladly make gum in gallon tanks.

H H H H

0= 000
DGulose

CH2 OH

1=001
DIdose
CHO

2=010
DGalactose
CHO

L.Fieser
H H HO H

CHO OH OH H OH
2

HO H HO H
2

H OH H OH

H HO HO H
2

OH H H OH

HO HO HO H

There is CH OH 3=011 also the L series, the DTalose mirror CHO image H structures H
2

OH

H OH
2

4=100CH OH

CH OH 5=101

CH 6=110 OH

CH 7=111 OH

25-11

Amino Sugars
x

Amino sugar: A sugar that contains an -NH2 group in place of an -OH group.
Only three amino sugars are common in nature N-Acetyl-D-glucosamine is a derivative of Dglucosamine.
H HO H H CHO NH2 H OH OH CH2OH CHO H2N 2 H HO H H OH H OH CH2OH CHO H NH2 HO H HO 2 H H OH CH2OH H HO H H CHO O NHCCH2 H OH OH CH2OH

DGlucosamine DMannosamine DGalactosamine

NAcetylD glucosamine

25-12

Physical Properties
x

Monosaccharides are colorless crystalline solids, very soluble in water, but only slightly soluble in ethanol.
sweetness relative to sucrose:
Sweetness Relativeto Carbohydrate Sucrose Fructose 22 .2 Invertsugar 22 .2 Sucrose(tablesugar) 2 2 .2 Honey 22 .2 Glucose 22 .2 Maltose 22 .2 Galactose 22 .2 Lactose(milksugar) 2 2 .2 Sweetness Relativeto Artificial Sweetener Sucrose Saccharin 22 2 AcesulfameK 22 2 Aspartame 22 2

25-13

Cyclic Structure
x

Monosaccharides have hydroxyl and carbonyl groups in the same molecule and those with five or more carbons exist almost entirely as five- and six-membered cyclic hemiacetals.
Anomeric carbon: The new stereocenter created as a result of cyclic hemiacetal formation. Anomers: Carbohydrates that differ in configuration at their anomeric carbons named and .

25-14

Haworth Projections
x

Haworth projections
Five- and six-membered hemiacetals are represented as planar pentagons or hexagons viewed through the edge. They are commonly written with the anomeric carbon on the right and the hemiacetal oxygen to the back right. The designation - means that the -OH on the anomeric carbon is cis to the terminal -CH2OH; - means that it is trans to the terminal -CH2OH.

25-15

Haworth Projections
CHO H OH HO H H OH CH2 OH
2

redrawtoshowtheOH oncarbon2 closetothe aldehydeoncarbon2

top

H 2 OH DGlucose

Lay molecule on side. cis,

CH2 OH H2 OH O H OH H C 2H HO H anomeric carbon OH

trans,

CH2 OH O OH() H H OH H HO H H OH DGlucopyranose (DGlucose)

CH2 OH O H H H + OH H HO OH() H OH DGlucopyranose ( DGlucose)

anomeric carbon

25-16

Haworth Projections
Six-membered hemiacetal rings are shown by the infix -pyran-. pyran Five-membered hemiacetal rings are shown by the infix -furan-. furan
O O

Furan

Pyran

25-17

Conformational Formulas
Five-membered rings are so close to being planar that Haworth projections are adequate to represent furanoses.
HOCH2 H H O H H HOCH2 H O OH () H

OH () H H OH OH OH H 2 DeoxyDribofuranose DRibofuranose (2 DeoxyDribose) (DRibose)

25-18

Conformational Formulas
Other monosaccharides also form five-membered cyclic hemiacetals. Here are the five-membered cyclic hemiacetals of Dfructose, a ketohexose.
2 2

HOCH2
2

CH2 OH HOCH2
2

O H HO H

CH2 OH
2

H HO

OH()

-DFructofuranose ( -DFructose)

C=O HO H 2 H OH 2 H OH 2 CH2 OH DFructose

2

O H HO H

OH ()
2

H HO

CH2 OH
2

-DFructofuranose (-DFructose)

25-19

Ascorbic Acid (Vitamin C)

x

L-Ascorbic acid (vitamin C) is synthesized both biochemically and industrially from D-glucose.
H HO H H CHO biochemial OH andindustrial H syntheses OH OH CH2OH CH2OH H OH O H HO O OH

DGlucose

LAscorbicacid (VitaminC)

25-20

Ascorbic Acid (Vitamin C)

L-Ascorbic acid is very easily oxidized to Ldehydroascorbic acid. Both are physiologically active and are found in most body fluids.
CH2OH H OH O H HO OH O oxidation reduction H H CH2OH OH O O O O

LAscorbicacid (VitaminC)

LDehydroascorbicacid

25-21

Conformational Formulas; to conversion

For pyranoses, the six-membered ring is more accurately represented as a chair conformation.
H OH HO HO H HO H OH H OH HO HO H H H OH H OH OH H O

Open chain form

DGlucopyranose (DGlucose) H OH HO HO H H

rotate about C-2 C-2 to bond H OH H OH OH O H HO HO HO OH OH H

H DGlucopyranose (DGlucose)

25-22

Conformational Formulas
The orientations of groups on carbons 1-5 in the Haworth and chair projections of -D-glucopyranose are up-down-up-down-up.
2 CH2 OH 2 2

H 2 OH HO
2

O OH() H
2 2

HO HO

CH2 OH
2 2 2

O OH 2 OH()

OH

DGlucopyranose (Haworthprojection)

-DGlucopyranose (chairconformation)

25-23

Mutarotation
x

Mutarotation: The change in specific rotation that occurs when an or form of a carbohydrate is converted to an equilibrium mixture of the two.
[]after %Presentat Monosaccharide [] Mutarotation Equilibrium Dglucose 2 2 +2.2 2 +22 2.2 Dglucose +2.2 2 +2.2 2 2 2 Dgalactose Dgalactose
HO HO CH2 OH O OH ()

+22 2.2 +2.2 2

+2.2 2 +2.2 2
HO HO

2 2 2 2
CH2OH O HO

OH DGlucopyranose []D22 +2.2 2

OH () DGlucopyranose 2 25-24 []D 2 +22 2

Hemiacetals and Acetals, carbonyls and alcohols

Addition reaction.

(Unstable in Acid; Unstable in base)

(Unstable in Acid; Stable in base) Substitution reaction

25-25

Glycosides, anomeric OH becomes OR, acetal formation.

x

Glycoside: A carbohydrate in which the -OH of the anomeric carbon is replaced by -OR.
methyl -D-glucopyranoside (methyl -D-glucoside)
glycosidic bond

CH2 OH CH2 OH CH2 OH O OH OH O OCH2 H H + H H H H H + CH2OH + OH H OH H OH H -H2O HO H HO OCH2 H HO H OH H OH H OH DGlucopyranose Methyl Dgluco Methyl Dgluco (-DGlucose) pyranoside pyranoside (MethylDglucoside) (MethylDglucoside)

25-26

Glycosides, acetals
x

Glycosidic bond: The bond from the anomeric carbon of the glycoside to an -OR group. Glycosides are named by listing the name of the alkyl or aryl group bonded to oxygen followed by the name of the carbohydrate with the ending -e replaced by -ide. -ide
methyl -D-glucopyranoside methyl -D-ribofuranoside

25-27

N-Glycosides
x

The anomeric carbon of a cyclic hemiacetal also undergoes reaction with the N-H group of an amine to form an N-glycoside.
N-glycosides of the following purine and pyrimidine bases are structural units of nucleic acids.
O HN O N H Uracil O N N H Cytosine NH2 HN O O CH2 N N NH2 N HN H2N N O N N H

N H Thymine

N H Adenine

Guanine

25-28

N-Glycosides
The -N-glycoside formed between D-ribofuranose and cytosine.
NH2 N HOCH2 H H HO O O H N a -Nglycosidic bond

H anomeric carbon OH

25-29

Reactions

25-30

Reduction to Alditols, aldehyde alcohol

x

The carbonyl group of a monosaccharide can be reduced to an hydroxyl group by a variety of reducing agents, including NaBH4 and H2/M.
HO HO CH2 OH O OH CHO H OH HO H H OH H OH CH2OH DGlucose CH2OH H OH HO H H OH H OH CH2OH DGlucitol (DSorbitol)

NaBH2

OH DGlucopyranose

An alditol
25-31

Other alditols
Other alditols common in the biological world are:
CH2OH H OH H OH CH2OH Erythritol CH2OH HO H HO H H OH H OH CH2OH DMannitol CH2OH H OH HO H H OH CH2OH Xylitol

25-32

Oxidations

Oxidation can be done in several ways. Tollens reagent (Ag+(NH3)2 or Benedicts solution (Cu2+ tartrate complex). Not synthetically useful due to side reactions. Bromine water oxidizes aldoses (not ketoses) to monocarboxylic acids (Aldonic Acids). Nitric Acid oxidizes aldoses to dicarboxylic acids (Aldaric acids). Enzyme catalyzed oxidation of terminal OH to carboxylic acid (Uronic Acid) Periodic Acid oxidizes and breaks C C bonds. Later for that. 25-33

Reducing Sugars
x

Sugars with aldehyde (or ketone group) in solution. The group can be oxidized and is detected with Tollens or Benedicts solution. Ketone groups converted to aldehyde via tautomeric shifts (later).

25-34

Problem with Tollens

x

2-Ketoses are also oxidized to aldonic acids in basic solution (Tollens).

CH2OH (2 ) C=O (CHOH) n CH2OH A2 ketose CHOH C-OH (2 ) (CHOH) n CH2OH Anenediol CHO CHOH (2 ) (CHOH) n CH2OH Analdose COOH CHOH (CHOH) n CH2OH Analdonicacid

Ketose to aldose conversion via keto enol tautomerism

Oxidation

Reducing sugar

25-35

Oxidation to Aldonic Acids: aldehyde carboxylic

x

The -CHO group can be oxidized to -COOH.

O HO HO CH2 OH O OH OH H HO H H OH oxidizing H OH agent H HO H OH basic H OH OH solution H OH CH2OH CH2OH DGlucose DGluconate C H O C O-

-DGlucopyranose ( -DGlucose)

25-36

Oxidation to carboxylic acids

CO2 H H HO H OH H OH OH CH2 OH H OH H OH OH CH2 OH

Br2water
CHO H HO H H

Aldonic Acid

HNO2
CO2 H H HO H H CO2 H OH

Aldaric Acid
H OH OH

25-37

Oxidation to Uronic Acids

x

Enzyme-catalyzed oxidation of the terminal -OH group gives a -COOH group.

CHO H OH enzymecatalyzed oxidation HO H H OH H OH CH2OH DGlucose H HO H H CHO OH COOH O H HO OH HO OH OH COOH DGlucuronicacid (auronicacid)

OH

25-38

Oxidation to Uronic Acids

In humans, D-gluconic acid is an important component of the acidic polysaccharides of connective tissue. It is also used by the body to detoxify foreign hydroxyl-containing compounds, such as phenols and alcohols; one example is the intravenous anesthetic propofol.
HO HO COO
-

O OH O

HO

Propofol

Aurinesolubleglucuronide
25-39

Oxidation by periodic acid, HIO4 or H5IO6

x

Periodic acid cleaves the C-C bond of a glycol.

OH C OH O -2 2O H + I OH C OH HO OH HO
A 2 diol ,2 Periodicacid

OH O I OH C O OH C O
Acyclicperiodic ester

C O C O

+ H2IO2
Iodicacid

25-40

Oxidation by HIO4
It also cleaves -hydroxyketones
H H C OH C O R H H H2IO2 H C O HO C O R

+ H2O

H C OH HO C OH

-Hydroxyketone

Hydrated intermediate

and -hydroxyaldehydes.
H C H C OH R -Hydroxyaldehyde + H2O

OH H C OH H C OH R

H2IO2

OH H C O H C O R 25-41

Hydrated intermediate

Examples. Identify each of the glucose derivatives.

A + 2 HIO2 yielded 2 HCO2 + HCHO + OHC-CO2 H H B + 2 HIO2 yielded 2 HCO2 + 2 H HCHO C + 2 HIO2 yielded 2 HCO2 + 2 H OHC-CO2 H
Analysis of A: 4 moles of periodic acid used. 4 bonds broken. Products: Formic acid from CHOH- or CHO-. Formaldehyde from CH2OHOHC-CO2H from CHOH-CO2H
H HO H H

CO2 H OH H OH OH CH2 25-42 OH

Another example
x

Oxidation of methyl -D-glucoside consumes two moles of HIO4 and produces one mole of formic acid, which indicates three adjacent C-OH groups.
periodicacidcleavage atthesetwobonds H HO HO CH2OH O OH
2 HIO4 2HIO
2

O O

C CH2OH O C H OCH2

OCH2

OH O C H

MethylDglucopyranoside

25-43

Osazones, Epimers

CHO CHOH

2 PhNHNH2

CH=NNHPh C=NNHPh

PhCHO
O

aldose

osazone

osone

25-44

Use of osazone in structure determination

Fischer found that (+) glucose and (+) mannose yielded the same osazone indicating that they differed only at the C2 configuration. Hence, if we know the configuration of (+) glucose we immediately have that of (+) mannose. Stereoisomers that differ in configuration at only one stereogenic center are called epimers. D-glucose and Dmannose are epimers. NNHPH
CHO H HO H H OH H OH OH CH2 OH PhHNN HO H H H OH OH CH2 OH HC HO HO H H CHO H H OH OH CH2 OH

D glucose

D mannose

25-45

Glucose Assay: diabetes (background)

x

The analytical procedure most often performed in the clinical chemistry laboratory is the determination of glucose in blood, urine, or other biological fluid.

25-46

Glucose Assay
x

The glucose oxidase method is completely specific for D-glucose.

25-47

Glucose Assay
The enzyme glucose oxidase is specific for -Dglucose. Molecular oxygen, O2, used in this reaction is reduced to hydrogen peroxide H2O2. The concentration of H2O2 is determined experimentally, and is proportional to the concentration of glucose in the sample. In one procedure, the hydrogen peroxide oxidizes otoluidine to a colored product, whose concentration is determined spectrophotometrically.

25-48

Killani-Fischer lengthening of chain

epimers
CHO HO H H H OH OH CH2 OH CN H HO H H OH H OH OH CH2 OH HO HO H H CN H H OH OH CH2 OH H CO2 H OH H OH OH CH2 OH HO HO H H CO2 H H H OH OH CH2 OH

HCN

aq acid

HO H H

D Arabinose
CHO H

CHO OH H OH OH HO HO H H H H OH OH CH 2 OH

As lactones Get both epimers.

Na

HO H H

CH 2 OH

25-49

Ruff Degradation shortening of chain

CHO H HO H H OH H OH OH CH2 OH H HO H H

CO2 H OH H OH OH CH2 OH H

CO2 )2Ca+2

Br2

OH H OH OH CH2 OH

CHO

CaCO 2

H2 2 O
HO H OH OH CH2 OH

HO H H

Fe+2
H H

25-50

Fischer proof of structure of glucose

Emil Fischer received the 1902 Nobel prize for determining the structure of glucose. What was available to him in 1888? Theory of stereoisomerism Ruff degradation Oxidation to aldonic and aldaric acids Killani-Fischer synthesis Various aldohexoses and aldopentoses

25-51

Fischer proof of structure of glucose

glucose known to be an aldohexose but of unknown structure
CHO

f our chiral centers. 2 stereoisomers, 2 2 pairs of enantionmers, 2 and 2 D L

OH
CH 2 OH

Fischer could not work with absolute conf igurations. He assumed that naturally occuring glucose was D. He had to work out the relationship of the other three OH.

25-52

Fischer started with the aldopentoses

One monosaccharide that was available was (-) arabinose, an aldopentose.
CHO

three chiral centers 2 stereoisomers = 2 pairs of enantiomers = 2 + 2 L D

OH
CH 2 OH

Again, Fischer could not work with absolute conf igurations. He assumed that naturally occuring (-) arabinose was D. He had to work out the relationship of the other two OH.

25-53

Experiments on (-) arabinose

Fact: Nitric acid oxidation of (-) arabinose yielded an optically active aldaric acid
CHO HO CO2 H

HNO2

OH CH 2 OH CO2 H

OH

Conclusion: (-) arabinose is either

CHO HO OH HO CHO

assumed partial structure of (-) arabinose

optically active

or

HO OH CH2 OH

Must be an OH here

OH CH2 OH

25-54

Use KF to get aldohexoses

Fact: Killani Fischer synthesis on (-) arabinose yielded (+) glucose and (+) mannose
CHO HO CHO OH HO OH CH2 OH OH CH2 OH OH CH2 OH HO CHO

K. F.

+ HO

partial structure of arabinose

mixture of + glucose and + mannose, both of unknown structure. Which is glucose is unknown.

25-55

Aldaric acids from glucose and mannose Fact: nitric acid oxidation of either glucose or mannose yields optically active aldaric acids. This locates the OH on C4 since both aldaric acids have to be active.
CHO OH HO OH OH CH 2 OH HO CHO CHO OH HO OH OH CH 2 OH HO OH CH 2 OH HO CHO

+ HO

+ HO
HO OH CH 2 OH

Each yields optically active aldaric acid.

yields optically inactive aldaric

yields optically active aldric

C4 OH on right

C4 OH on left

25-56

Which is glucose??

CHO OH HO OH OH CH2 OH HO

CHO

+ HO
OH OH CH2 OH

Which one, A or B, is glucose is determined by preparing the aldaric acids (dicarboxylic acids).

25-57

Final piece of data

Fact: the aldaric acid from (+)glucose is also produced by nitric acid oxidation of a different aldohexose, (+)gulose.
CHO HO HO OH OH CHO OH OH CH2 OH

CHO H HO H H OH H OH OH CH2 OH

CO2 H OH

CH2 OH OH

HNO2 HO
OH OH CO2 H

HNO2 HO

A structure of glucose

aldaric acid f rom A.

(+) gulose which turns out to be an L aldohexose

Aldaric acid f rom B comes only f rom B, (+) mannose

25-58

Where are we?

x

We have determined the straight chain structure of (+) glucose. But certain data indicates the problem is not yet solved. Glucose does not give some reactions characteristic of aldehydes
A qualitative test, Schiff test, for aldehydes is negative. Bisulfite addition products cannot be made

x x

Mutarotation changes specific rotation. Glucose is converted into two acetals (the methyl D-glucosides), not hemiacetals, by reaction with one mole of methanol (acid).
Conclude: glucose is a cyclic hemiacetal.
25-59

Now to determine ring size.

We can methylate the various OH groups, converting them into OMe. Two kinds of OH OH at anomeric carbon OH on backbone One of the backbone OH groups may be bonded to the anomeric carbon to form a ring. We seek to detect which one. First review characteristics of hemiacetals and acetals.

25-60

Hemiacetals and Acetals, carbonyls and alcohols

Addition reaction.

(Unstable in Acid; Unstable in base)

(Unstable in Acid; Stable in base) Substitution reaction

25-61

Methylation to find ring size.

H HO H H HO HO H H OH H H O HO H HO HO H OH H
H

CH2 OH
OH

H2 CO H

(CH2 2 2 O) SO , NaOH
OCH 2
H2 CO H2 CO H

dry HCl

OCH 2 OCH2 H

Methyl D glucoside
CHO
H2 CO H

H
H O OH H H OCH2 H

OCH2 H OCH2 OH OCH2

dil HCl
H2 CO H2 CO

H2 CO

C2 C2 cleavage C2 C2 cleavage
OCH2 H OCH2

H H

CO2 H H OCH2 H CO 2

CO2 H H H2 CO CO2 H

oxidation HNO2

H CO2 H

C2 C2 cleavage

C2 C2 cleavage

The observed 4 carbon and 5 carbon dicarboxylic acids indicate free OH was on C5.
25-62

Conformation of the pyranose ring.

Ring flips can occur. Generally the conformation with large groups equatorial dominate.
HOH 2 C HO HO HO O OH CH 2 OH OH O OH

more stable

OH

OH

less stable

-D glucopyranose

Generally the CH2OH should be made equatorial

25-63

Extreme case: a-D-Idopyranose

axial
OH HOH 2 C H H H HO H HO HO H HO CH 2 OH OH O O OH OH

more stable

-D-Idopyranose

25-64

disaccharides
x x x

Sucrose, table sugar Maltose, from barley Lactose, milk sugar

25-65

Sucrose, table sugar

x

Table sugar, obtained from the juice of sugar cane and sugar beet.

-1, -2 bond

25-66

Lactose
x

The principle sugar present in milk, 5 10%.

25-67

Maltose
x

From malt, the juice of sprouted barley and other cereal grains.

25-68

Structure Determinatin of (+) Maltose

x x x

Experimental Facts C12H22O11 Positive for Tollens and Fehlings solution, reducing sugar Reacts with phenylhydrazine to yield osazone, C12H20O9(NNHC6H5)2

Oxidizes by bromine water to monocaboxylic acid. x Exists in two forms which undergo mutarotation. Consistent with two aldoses linked together with one hemiacetal group.
25-69

More data..
x

Maltose undergoes hydrolysis with aq. acid or maltase to yield two D (+) glucose units. Two glucose units joined together: glucose acetal linkage (glucoside) glucose hemiacetal. Maltase hydrolysis is characteristic of glucosides. Conclude something like
CH 2 OH CH 2 OH

OH

O
25-70

How to proceed..
Label the rings and label the free OH groups.
CH 2 OH CH 2 OH

Br2 H2 , O O
OH CH 2 OH

CH 2 OH

OH CO 2 H
O OH

HO

Me2 2 SO base OMe

unmethylated O

OMe OMe CO2 H

aq acid

Next Slide

f ree OH methylated

MeO

f ree OH methylated

OMe

25-71

Hydrolysis products
CHO H MeO H H OMe H OMe OH CH 2 OMe H MeO H H CO 2 H OH H OH OMe CH 2 OMe

Used in hemiacetal link.

Point of attachment to the other glucose unit.

Not the reducing aldohexose unit (not the carboxylic acid).

This glucose derivative was the free CHO unit, the Structure on next reducing sugar. slide.
25-72

Maltose
H OH H HO HO H H OH O HO H H OH HO H H O H O H OH

25-73

Starch
x

Starch is used for energy storage in plants

It can be separated into two fractions; amylose and amylopectin; each on complete hydrolysis gives only D-glucose. Amylose Amylose: A polysaccharide composed of continuous, unbranched chains of up to 4000 D-glucose units joined by -1,4-glycosidic bonds. Amylopectin Amylopectin: A highly branched polymer of D-glucose; chains consist of 24-30 units of D-glucose joined by 1,4-glycosidic bonds and branches created by -1,6glycosidic bonds.

25-74

Glycogen
x

Glycogen is the reserve carbohydrate for animals.

Like amylopectin, glycogen is a nonlinear polymer of D-glucose units joined by -1,4- and -1,6-glycosidic bonds bonds. The total amount of glycogen in the body of a wellnourished adult is about 350 g (about 3/4 of a pound) divided almost equally between liver and muscle.

25-75

Cellulose
x

Cellulose: A linear polymer of D-glucose units joined by -1,4-glycosidic bonds.

It has an average molecular weight of 400,000 g/mol, corresponding to approximately 2800 D-glucose units per molecule. Both rayon and acetate rayon are made from chemically modified cellulose.

25-76

Acidic Polysaccharides
x

Hyaluronic acid: An acidic polysaccharide present in connective tissue, such as synovial fluid and vitreous humor.

25-77

Acidic Polysaccharides
x

Heparin
Its best understood function is as an anticoagulant. Following is a pentasaccharide unit of heparin.

25-78

An example..
A synthetic polysaccharide is composed of three monosaccharides units in the following order: (D-glucpyranose) (L-fructofuranose) (D-altropyranose). The linkages between the units and the structures of the individual D units are given below where the wavy lines are used to avoid specifying configuration.
CH2 OH CH2 OH OH O OH OH OH OH O OH CH 2 OH OH OH OH

CH2 OH O OH

OH

D-glucopyranose
O

D-f ructof uranose

D-altropyranose
O

2,6 linkage ,2 2 linkage D-Altrose D-Glucose L-Fructose

anomer

Add all substituents to the rings and show the linkages between the units. You must show stereochemistry clearly.

25-79

Solution
CH2 OH CH2 OH OH O OH OH OH OH O OH CH 2 OH OH OH OH CH2 OH O OH

OH

D-glucopyranose
CH 2 OH

D-f ructof uranose

CH 2 OH CH
2

D-altropyranose
O
OH OH
OH

O
OH

OH
CH2 OH

O
CH 2 OH OH 2 CH OH

OH
H

OH
OH

OH
OH

2,6 linkage OH ,2 2 linkage D-Altrose D-Glucose L-Fructose

anomer

Now L fructose the 1,4 link D-Altrose the ano mer Now the 2,6 Now First the D glucose Now Now 25-80