Professional Documents
Culture Documents
25 Carbohydrates
25 Carbohydrates
Chapter 25
25-1
Carbohydrates
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
glucose
glycogen (liver)
25-3
Monosaccharides
Monosaccharides
of carbon atoms:
N ame Trios e Tetros e Pen tos e Hexose Heptose Octose
25-4
Monosaccharides
There
These
compounds are referred to simply as trioses, tetroses, and so forth tellling the number of carbon atoms present.
25-5
CHO H C OH
CHO H
.
OH
25-6
D,L Monosaccharides
In
1891, Emil Fischer made the arbitrary assignments of D- and L- to the enantiomers of glyceraldehyde.
CHO H OH CH2 OH CHO HO H CH2 OH
D -Glyce raldehyde L-Glyce raldehyde (R)-Glyceraldehyde (S )-Glyce raldehyde []25 = +13.5 []25 = -13.5
D D
25-7
D,L Monosaccharides
According
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
D-aldotetroses
D,L Monosaccharides
The
0= 000
1=001
2=010
L.Fieser
4=100
5=101
6=110
7=111
25-11
Amino Sugars
Amino
25-12
Physical Properties
Monosaccharides
are colorless crystalline solids, very soluble in water, but only slightly soluble in ethanol.
sweetness relative to sucrose:
Carbohydrate S w eetness Relative to S ucrose 1.74 1.25 1.00 0.97 0.74 0.33 0.32 0.16 Artificial Sw eetener Saccharin Aces ulfame-K Asp artame S w eetness Relative to S ucrose 450 200 160
Fructos e In vert su gar Sucrose (tab le sugar) Hon ey Glucose Maltos e Galactose Lactose (milk s ugar)
25-13
Cyclic Structure
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 b.
25-14
Haworth Projections
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 b- 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
1
H 5 OH CH2 OH D -Glucose
top
trans,
anomeric carb on
25-16
Haworth Projections
Six-membered hemiacetal rings are shown by the infix -pyran-. Five-membered hemiacetal rings are shown by the infix -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 H HOCH2 H O H H OH ( b)
25-18
Conformational Formulas
Other monosaccharides also form five-membered cyclic hemiacetals. Here are the five-membered cyclic hemiacetals of Dfructose, a ketohexose.
1 2
CH 2 OH HOCH2
5
HOCH2
5
O H HO H
CH 2 OH
2
H HO
OH ( )
-D -Fructofuranose ( - D -Fructos e)
O H HO H
OH ( b)
2
H HO
CH 2 OH
1
25-19
25-22
Conformational Formulas
The orientations of groups on carbons 1-5 in the Haworth and chair projections of b-D-glucopyranose are up-down-up-down-up.
6 CH OH 2 6
H
4
O H
H OH
3
OH(b)
1
CH2 OH O
5 3 2
HO HO
HO H
H
2
OH( b) OH 1
OH
25-23
Mutarotation
Mutarotation:
The change in specific rotation that occurs when an or b form of a carbohydrate is converted to an equilibrium mixture of the two.
[] after % Present at Mon os accharide [] Mutarotation Equ ilib riu m -D -glu cose 36 +52.7 +112.0 b-D -glucos e +18.7 +52.7 64 -D -galactos e b-D -galactose
CH2 OH O OH ( b)
+150.7 +52.8
+80.2 +80.2
HO HO
28 72
CH2 OH O
HO HO
HO
Substitution reaction
CH2 OH CH2 OH CH2 OH O OH OH O OCH3 H H + H H H H H + CH3 OH + OH H OH H OH H -H2 O HO H HO OCH3 H HO H OH H OH H OH b-D -Glu copyran os e Methyl b-D -glu coMeth yl -D -glu co(b-D -Glu cose) pyran os ide p yranosid e ( Methyl b-D -glucos ide) (Methyl -D -glucos ide)
25-26
Glycosides, acetals
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.
methyl b-D-glucopyranoside methyl -D-ribofuranoside
25-27
N-Glycosides
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 U racil O N N H Cytosine NH2 HN O O CH3 N N NH2 N HN H2 N N O N N H
N H Thymine
N H Ad enin e
Guan ine
25-28
N-Glycosides
The b-N-glycoside formed between D-ribofuranose and cytosine.
NH2 N HOCH2 H H HO O O H H OH anomeric carbon N a b-N -glycosid ic bond
25-29
Reactions
25-30
carbonyl group of a monosaccharide can be reduced to an hydroxyl group by a variety of reducing agents, including NaBH4 and H2/M.
CH2 OH O OH CHO H OH HO H H OH H OH CH2 OH D -Glu cose CH2 OH H OH HO H H OH H OH CH2 OH D -Glucitol (D -Sorbitol)
HO HO
NaBH4
An alditol
25-31
Other alditols
Other alditols common in the biological world are:
CH2 OH HO H HO H H OH H OH CH2 OH D -Mann itol CH2 OH H OH HO H H OH CH2 OH 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
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
Oxidation
Reducing sugar
25-35
25-37
OH
25-38
HO OHO - 2 H O C OH 2 + I C OH HO OHOH
A 1,2-diol Periodic aci d
OH O I C O OHOH C O
A cycli c pe ri odi c es ter
C O C O + H 3 IO 4
Iodic acid
25-40
Oxidation by HIO4
It also cleaves -hydroxyketones
H H C OH C O R H H H5 IO 6 H C HO C R O O
+ H2 O
H C OH HO C OH R
-Hydroxyketone
Hydrated in termediate
and -hydroxyaldehydes.
O H C H C OH R -Hydroxyald ehyde + H2 O OH H C OH H C OH R Hydrated in termediate H5 IO6 OH H C O H C O R
25-41
CO2H OH
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
HO
OH
OH
CH2OH
25-42
Another example
Oxidation
of methyl b-D-glucoside consumes two moles of HIO4 and produces one mole of formic acid, which indicates three adjacent C-OH groups.
periodic acid cleavage at thes e tw o b on ds H HO HO CH2 OH O OH
2 HIO4 2 HIO
5
O O
C CH2 OH O C H OCH3
OCH3
OH O C H
25-43
Osazones, Epimers
O CHO
3 PhNHNH2
CH=NNHPh
PhCHO
C=NNHPh O
CHOH
aldose
osazone
osone
25-44
HO
HO
HO
OH
OH
OH
OH
OH
OH
CH2OH
CH2OH
CH2OH
D glucose
D mannose
25-45
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
The
25-47
Glucose Assay
The enzyme glucose oxidase is specific for b-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
25-49
25-50
25-51
25-52
25-53
Must be an OH here
25-54
HO
OH
K. F.
HO
HO
OH OH OH
CH2OH
CH2OH
CH2OH
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.
C4 OH on right
C4 OH on left
25-56
Which is glucose??
CHO HO
CHO
OH
HO
+
OH
HO
Which one, A or B, is glucose is determined by preparing the aldaric acids (dicarboxylic acids).
OH
OH
OH
CH2OH
CH2OH
25-57
25-58
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
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
25-60
Substitution reaction
The observed 4 carbon and 5 carbon dicarboxylic acids indicate free OH was on C5.
25-62
25-64
disaccharides
Sucrose,
25-65
sugar, obtained from the juice of sugar cane and sugar beet.
25-66
Lactose
The
25-67
Maltose
From
25-68
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. Exists in two forms which undergo mutarotation. Consistent with two aldoses linked together with one hemiacetal group.
25-69
More data..
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
25-70
How to proceed..
Label the rings and label the free OH groups.
Next Slide
25-71
Hydrolysis products
Point of attachment to the other glucose unit.
Used in hemiacetal link. Not the reducing aldohexose unit (not the carboxylic acid).
This glucose derivative was the free CHO unit, the Structure on next reducing slide. sugar.
25-72
Maltose
25-73
Starch
Starch
It can be separated into two fractions; amylose and amylopectin; each on complete hydrolysis gives only D-glucose. Amylose: A polysaccharide composed of continuous, unbranched chains of up to 4000 D-glucose units joined by -1,4-glycosidic bonds. 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
Glycogen
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
Cellulose:
25-76
Acidic Polysaccharides
Hyaluronic
acid: An acidic polysaccharide present in connective tissue, such as synovial fluid and vitreous humor.
25-77
Acidic Polysaccharides
Heparin
25-78
An example..
A synthetic polysaccharide is composed of three monosaccharides units in the following order: (D-glucpyranose) (L-fructofuranose) (Daltropyranose). 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.
Add all substituents to the rings and show the linkages between the units. You must show stereochemistry clearly.
25-79
Solution
Now L fructose Now mer First the D glucose the b 1,4 link Now thethe b ano 25-80 Now Now D-Altrose 2,6