Introduction to Biochem

 Hello 11I, I am Erlyn Jessie Dy, your instructor in Biochemistry. I will try my best to
have a synchronous session with you by next week, as of now I am still dealing
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chatbox if you have any questions and I will deal with it ASAP.

 Please do the assignment in slide 20 about blood typing. Submit it within this week.
Save your file with your surname and send it to erlyndy@davaodoctors.edu.ph
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Scoring is 60-40, example passing score in 10-item test will 6.
60% of your grades will be taken from the Lecture and 40% from the Lab.

CHAPTER 20 CARBOHYDRATES

SOURCE OF CARBOHYDRATES (Cellulose and Starch)

DEFINITION OF CARBOHYDRATES

 Old – hydrate of carbon

 New – polyhydroxyaldehyde or polyhydroxyketone

CLASSIFICATION OF CARBOHYDRATES

 Saccharides – Latin: saccharum, sugar

  Monosaccharides

 Oligosaccharides – 2 (disaccharides) to 10 simple sugars

 Polysaccharides

CHIRALITY

o Handedness in molecules – mirror image

o Superimposable
o nonsuperimposable
o Chiral and achiral
STEREOISOMERS/ISOMERS

o Contains chiral carbon

o Enantiomers – mirror image

o Diastereomers – not mirror image

o Epimers

Fischer Projection

o German Chemist Hermann Emil Fischer (1852 – 1919)

NOMENCLATURE OF MONOSACCHARIDES

o Suffix – ose

o Prefixes – tri -, tetr-, pent –

o Aldoses

o Ketoses

D-Glyceraldehyde, Dihydroxyacetone

Glucose

o Grape Sugar
o Dextrose
o Blood Sugar (70 – 100mg/dL) , insulin and glucagon (65 -110mg/dL)
Galactose

o Brain sugar

Fructose
Levulose
Fruit sugar

CARBOHYDRATES

 Carbohydrate: a polyhydroxyaldehyde or
polyhydroxyketone, or a
substance that gives these compounds on hydrolysis.

 Monosaccharide: a carbohydrate that cannot be hydrolyzed to a simpler carbohydrate.

 Monosaccharides have the general formula C H O , where n varies from
n 2n n

3 to 7.

 Aldose: a monosaccharide containing an aldehyde group.

  Ketose: a monosaccharide containing a ketone group.
Ribose

Amino Sugars

MONOSACCHARIDES

o Monosaccharides are classified by their number of carbon atoms.

Name Formula
Triose C3 H6 O3
Tetrose C4 H8 O4
Pentose C5 H1 0 O5
Hexose C6 H1 2 O6
Heptose C7 H1 4 O7
Octose C8 H1 6 O8

o There are only two trioses:

CHO CH2 OH
CHOH C= O
CH2 OH CH2 OH  Often aldo-
Glyceraldehyde Dihydroxyacetone and keto- are omitted
(an aldotriose) (a ketotriose)
 and these compounds are referred to simply as trioses.

 Although “triose” does not tell the nature of the carbonyl group, it at
least tells the number of carbons.

o Glyceraldehyde, the simplest aldose, contains a stereocenter and exists as a pair

of enantiomers.

CHO CHO

H C OH HO C H

CH2 OH CH2 OH

CYCLIC STRUCTURE

o Aldehydes and ketones react with alcohols to form hemiacetals.

hemiacetals

 Cyclic hemiacetals form readily when the hydroxyl and carbonyl groups are part of the
same molecule and their interaction can form a five- or six-membered ring.
O redraw to show
1 -OH and -CHO
4
H close to each other
O-H
4-Hydroxypentanal 1 H H
4
C
O O O O-H
H A cyclic hemiacetal

HAWORTH PROJECTIONS

o D-Glucose forms these cyclic hemiacetals.

 1
CHO redraw to show the -OH CH2 OH
H OH on carbon-5 close to the 5
H OH
HO H aldehyde on carbon-1 O
H
OH H C1
H OH HO H
5
H OH H OH
CH2 OH
D-Glucose CH2 OH CH2 OH anomeric
H O OH (  ) H O H carbon
H + H
OH H OH H
HO H HO OH(  )
H OH H OH
-D-Glucopyranose -D-Glucopyranose
(-D-Glucose) ( -D-Glucose)

HAWORTH PROJECTIONS

 A five- or six-membered cyclic hemiacetal is represented as a planar ring, lying roughly

perpendicular to the plane of the paper.

 Groups bonded to the carbons of the ring then lie either above or below the plane of the
ring.

 The new carbon stereocenter created in forming the cyclic structure is called an
anomeric carbon.
carbon

 Stereoisomers that differ in configuration only at the anomeric carbon are called
anomers.
anomers

 The anomeric carbon of an aldose is C-1; that of the most common ketoses is C-2.
 In the terminology of carbohydrate chemistry,

o β means that the -OH on the anomeric carbon is on the same side of the ring as
the terminal -CH2OH.

o α means that the -OH on the anomeric carbon is on the side of the ring opposite
from the terminal -CH2OH.   
o A six-membered hemiacetal ring is called a pyranose,
pyranose and a five-membered
hemiacetal ring is called a furanose.
furanose

O O
Furan Pyran
  Aldopentoses also form cyclic hemiacetals.
 The most prevalent forms of D-ribose and other pentoses in the biological world are
furanoses.

HOCH2 H HOCH2 OH ()

O O
H H H H
H OH () H H
OH OH OH H
-D-Ribofuranose -2-Deoxy-D-ribofuranose
(-D-Ribose) (-2-Deoxy-D-ribose)

 The prefix “deoxy” means “without oxygen.”

 D-Fructose (a 2-ketohexose) also forms a five-membered cyclic hemiacetal.
1
HOCH2 O CH2 OH
5 H HO 2

H OH( )
HO H 1
CH2 OH
2
 -D-Fructofuranose C=O HOCH2 O OH (  )
( - D-Fructose) HO H
5 H HO 2
H OH H CH2 OH
H5 OH HO H 1

CH2 OH
D-Fructose  - D-Fructofuranose
(- D-Fructose)
MUTAROTATION

o Mutarotation: the change in specific rotation that accompanies the equilibration of

α- and β-anomers in aqueous solution.

 Example: when either -D-glucose or -D-glucose is dissolved in water, the

specific rotation of the solution gradually changes to an equilibrium value of +52.7°,
which corresponds to 64% beta and 36% alpha forms.

CH2 OH CH2 OH CH2 OH

HO O HO OH HO O
HO HO O HO
OH C
OH HO HO
H OH
-D-Glucopyranose Open-chain form -D-Glucopyranose
25 25
[] D = + 18.7° [] D = + 112°

Physical Properties
 o Monosaccharides are colorless crystalline solids, very soluble in water, but only
slightly soluble in ethanol

 Sweetness relative to sucrose:

Sweetness Sweetness
Relative to Artificial Relative to
Carbohydrate Sucrose Sweetener Sucrose
fructose 1.74 saccharin 450
sucrose (table sugar) 1.00 acesulfame-K 200
honey 0.97 aspartame 180
glucose 0.74
maltose 0.33
galactose 0.32
lactose (milk sugar) 0.16

FORMATION OF GLYCOSIDES

o Treatment of a monosaccharide, all of which exist almost exclusively in cyclic

hemiacetal forms, with an alcohol gives an acetal.
anomeric
CH2 OH carbon
H O OH +
H H
OH H + CH3 OH
-H2 O
HO H
H OH glycosidic
CH2 OH bond CH2 OH
-D-Glucopyranose
O OCH3 H OH
(-D-Glucose) H H
H
OH H + OH H
HO H HO OCH3
H OH H OH
Methyl -D-glucopyranoside Methyl -D-glucopyranoside
(Methyl -D-glucoside) (Methyl -D-glucoside)
Formation of Glycosides

 A cyclic acetal derived from a monosaccharide is called a glycoside.

glycoside

 The bond from the anomeric carbon to the -OR group is called a glycosidic bond.
bond

 Mutarotation is not possible in a glycoside because an acetal, unlike a hemiacetal, is

not in equilibrium with the open-chain carbonyl-containing compound.

 Glycosides are stable in water and aqueous base, but like other acetals, are
hydrolyzed in aqueous acid to an alcohol and a monosaccharide.
  Glycosides are named by listing the alkyl or aryl group bonded to oxygen followed by
the name of the carbohydrate in which the ending -e
e is replaced by -ide.
-ide
Reduction to Alditols

o The carbonyl group of a monosaccharide can be reduced to an hydroxyl group

by a variety of reducing agents, including NaBH4 (Sodium borohydride) and H2 in the
presence of a transition metal catalyst.

 The reduction product is called an alditol.

alditol
CHO CH2 OH
CH2 OH H OH H OH
HO O HO H HO H
HO NaBH4
OH H OH H OH
OH H OH H OH
-D-Glucopyranose CH2 OH CH2 OH
D-Glucose D-Glucitol
(D-Sorbitol)
SORBITOL

 Sugar substitute – use in dietary foods, ice cream, drinks, sugar free chewing
gum, cough syrup

 Laxative

Reduction to Alditols

 Sorbitol is found in the plant world in many berries and in cherries, plums, pears,
apples, seaweed, and algae.

 It is about 60 percent as sweet as sucrose (table sugar) and is used in the

manufacture of candies and as a sugar substitute for diabetics.

 These three alditols are also common in the biological world.

CH2 OH
HO H CH2 OH
CH2 OH HO H H OH
H OH H OH HO H
H OH H OH H OH
CH2 OH CH2 OH CH2 OH
Erythritol D-Mannitol Xylitol

Erythritol, Mannitol, Xylitol

  Substitute for sugar

 Mannitol – facilitating agent for brain surgery

 Xylitol – tooth friendly

Oxidation to Aldonic Acids

 The aldehyde group of an aldose is oxidized under basic conditions to a carboxylate

anion.

 The oxidation product is called an aldonic acid.

acid
 A carbohydrate that reacts with an oxidizing agent to form an aldonic acid is
classified as a reducing sugar (it reduces the oxidizing agent).
O H O O-
C C
CH2 OH H OH oxidizing H OH
HO O HO H agent HO H
HO
H OH basic H OH
OH
OH H OH solution H OH
CH2 OH CH2 OH
- D-Glucopyranose D-Glucose D-Gluconate
( - D-Glucose)

Oxidation to Uronic Acids

 Enzyme-catalyzed oxidation of the primary alcohol at C-6 of a hexose yields a

uronic acid.
acid
o Enzyme-catalyzed oxidation of D-glucose, for example, yields D-glucuronic acid.
CHO CHO
enzyme-
H OH H OH
catalyzed COOH
HO H HO H O
oxidation HO
H OH H OH HO OH
H OH H OH OH
CH2 OH COOH
D-Glucose D-Glucuronic acid
(a uronic acid)
D-Glucuronic Acid

 D-Glucuronic acid is widely distributed in the plant and animal world.

 In humans, it is an important component of the acidic polysaccharides of connective
tissues.

 It is used by the body to detoxify foreign phenols and alcohols; in the liver, these
compounds are converted to glycosides of glucuronic acid and excreted in the urine.
 COO-
HO O
HO HO O
OH

Propofol A urine-soluble glucuronide

Phosphate Esters

 Mono- and diphosphoric esters are intermediates in the metabolism of

monosaccharides.

 For example, the first step in glycolysis is conversion of D-glucose to α-D-glucose

6-phosphate.
 Note that at the pH of cellular and intercellular fluids, both acidic protons of a
diphosphoric ester are ionized, giving it a charge of -2.
CHO O
-
H OH O P O-
HO H O
H OH CH2
O
H OH O HO
HO
CH2 O-P- O -
HO
O- OH
D-Glucose 6-phosphate -D-Glucose 6-phosphate

Disaccharides

 Sucrose (table sugar)

 Sucrose is the most abundant disaccharide in the biological world; it is obtained
principally from the juice of sugar cane and sugar beets.

 Sucrose is a nonreducing sugar.

CH2 OH CH2 OH a unit of -D-
O O glucopyranose
HO
OH 1 HO 1 -1,2-glycosidic bond
HO OH
OH O HOCH2 O a unit of -D-
HOCH2 O
O fructofuranose
HO 2 HO 2

CH2 OH 1
CH2 OH
1
OH OH

Disaccharides

 Lactose
  Lactose is the principal sugar present in milk; it makes up about 5 to 8 percent of
human milk and 4 to 6 percent of cow's milk.

 It consists of D-galactopyranose bonded by a β-1,4-glycosidic bond to carbon 4

of D-glucopyranose.
 Lactose is a reducing sugar.
CH2 OH
O OH OH -1,4-glycosidic bond
4 CH2 OH
CH2 OH OH O CH2 OH
OH O O 4
HO 1 O O
OH 1
OH OH HO OH
OH
OH

Disaccharides

 Maltose
 Present in malt, the juice from sprouted barley and other cereal grains.
 Maltose consists of two units of D-glucopyranose joined by an α-1,4-glycosidic bond.
 Maltose is a reducing sugar.

-1,4-glycosidic
1 4 CH2 OH CH2 OH bond
O
HOCH2 O O OH HO
O OH HO 1
OH OH 4 CH2 OH
HO O O
HO HO OH
OH OH
POLYSACCHARIDES
Polysaccharide: a carbohydrate consisting of large numbers of monosaccharide units
joined by glycosidic bonds.
Starch: a polymer of D-glucose.
Starch can be separated into amylose and amylopectin.
Amylose is composed of unbranched chains of up to 4000 D-glucose units joined by
α-1,4-glycosidic bonds.
Amylopectin contains chains up to 10,000 D-glucose units also joined by α-1,4-
glycosidic bonds; at branch points, new chains of 24 to 30 units are started by α-
1,6-glycosidic bonds.

Polysaccharides
Figure 20.3 Amylopectin.
Polysaccharides
Glycogen is the energy-reserve carbohydrate for animals.
Glycogen is a branched polysaccharide of approximately 106 glucose units joined by
α-1,4- and α-1,6-glycosidic bonds.
The total amount of glycogen in the body of a well-nourished adult human is about
350 g, divided almost equally between liver and muscle.

Polysaccharides

 Cellulose is a linear polysaccharide of D-glucose units joined by β-1,4-glycosidic bonds.

 It has an average molecular weight of 400,000 g/mol, corresponding to
approximately 2200 glucose units per molecule.

 Cellulose molecules act like stiff rods and align themselves side by side into well-
organized water-insoluble fibers in which the OH groups form numerous
intermolecular hydrogen bonds.

 This arrangement of parallel chains in bundles gives cellulose fibers their high
mechanical strength.

 It is also the reason why cellulose is insoluble in water.

Polysaccharides

• Figure 20.4 Cellulose is a linear polymer containing as many as 3000 units of D-glucose
joined by β-1,4-glycosidic bonds.
 Cellulose (cont’d)

 Humans and other animals cannot use cellulose as food because our digestive
systems do not contain β-glucosidases, enzymes that catalyze hydrolysis of β-
glucosidic bonds.

 Instead, we have only α-glucosidases; hence, the polysaccharides we use as

sources of glucose are starch and glycogen.

 Many bacteria and microorganisms have β-glucosidases and can digest cellulose.
 Termites have such bacteria in their intestines and can use wood as their principal
food.

 Ruminants (cud-chewing animals) and horses can also digest grasses and hay.
Acidic Polysaccharides

 Acidic polysaccharides: a group of polysaccharides that contain carboxyl groups and/or

sulfuric ester groups, and play important roles in the structure and function of connective
tissues.

 There is no single general type of connective tissue.

 Rather, there are a large number of highly specialized forms, such as cartilage,
bone, synovial fluid, skin, tendons, blood vessels, intervertebral disks, and cornea.

 Most connective tissues are made up of collagen, a structural protein, in

combination with a variety of acidic polysaccharides.
Acidic Polysaccharides

 Hyaluronic acid
 contains from 300 to 100,000 repeating units.
 is most abundant in embryonic tissues and in specialized connective tissues
such as synovial fluid, the lubricant of joints in the body, and the vitreous of the eye
where it provides a clear, elastic gel that maintains the retina in its proper position
 D-glucuronic acid N-Acetyl-D-glucosamine

COO
-
4 CH2 OH
4
O HO O
1 O O 1
HO 3
3
OH NH
C
H3 C O
The repeating unit of hyaluronic acid
Acidic Polysaccharides

 Heparin:
Heparin a heterogeneous mixture of variably sulfonated polysaccharide chains,
ranging in molecular weight from 6,000 to 30,000 g/mol.

Acidic Polysaccharides

 Heparin (cont’d)

 Heparin is synthesized and stored in mast cells of various tissues, particularly the
liver, lungs, and gut.

 The best known and understood of its biological functions is its anticoagulant
activity.
 It binds strongly to antithrombin III, a plasma protein involved in terminating the
clotting process.Carbohydrates
Carbohydrates