9.

Carbohydrates

Chapter 16
 CARBOHYDRATES

Contain C, H, O only
CXH2YOY = CX(H2O)Y
i.e hydrates of carbon

most common names end in '-----ose'

 Carbohydrates

General Structural Features

Usually 5/6 membered rings with C and one O

Many -OH groups

 water soluble (simple ones )
 easily broken down for energy
(already partly 'oxidized')
From Monosaccharides to Polysaccharides

The root sacchar- comes from the

Latin saccharum, "sugar".

A monosaccharide is the smallest molecular

unit of a carbohydrate.
Glucose, the prototypical monosaccharide, is the
most abundant organic molecule on earth.
 A disaccharide is a molecule formed from a
combination of two monosaccharides, eg.
sucrose

A polysaccharide is a molecular chain (maybe

branched) of hundreds / thousands of mono-
saccharides, eg. cellulose
 Common Carbohydrates
Carbohydrate Formula
Monosaccharides, C6(H2O)6
Glucose (blood sugar, grape sugar, dextrose) C6H12O6
Fructose ( levulose ) C6H12O6
Galactose C6H12O6

Disaccharides, C12(H2O)11
Sucrose (table sugar,beet sugar, cane sugar) C12H22O11
Maltose (malt sugar) C12H22O11
Cellobiose C12H22O11
Lactose (milk sugar ) C12H22O11

Polysaccharides, Cx(H2O)y
Starch
Glucose – a 2,3,4,5,6-pentahydroxy hexanal

C6H12O6 – a(aldo)hexose
6 6
HO HO
5 H 5
O O
4 O 4
HO 1 HO OH
1

3 2 3 2

HO OH HO OH

open chain cyclic

(6 mem. ring = pyran)
Glucose – single then soluble
Polysaccharides – the Glycosidic Linkage

HO + HO
O O O O
HO OH HO OH O
+ H 2O

HO OH HO OH
monosaccharides glycosidic linkage

O O O
* O O O O n*

starch = 1,4 linkages = cellulose

 STARCHES
Plant :
Amylose -straight chain (~200 -D glucose
units)
 Amylopectin - branched every ~25 units
(1000+ -D glucose units)
 Dextrins -partial breakdown of amylopectin
(food additives , paste , fabric finishes )
Animal :
 Glycogen
-branches every~12 units
-short-term energy in body (liver & muscle).
More Branching = Faster ‘Breakdown’

Amylopectin Glycogen
 Amylose Helical Structure
• Left hand helix (partial)
 Iodine test for Starch
• Helical structure of amylose holds the I 3-
ion; linear cellulose does not
 Carbohydrates
The Most Common Energy Source

Chemical Breakdown / Reaction = Digestion

H2O H2O H2O

Complex  Dextrins  Simple  Mono-
(starch) (glucose)

O2
 acetate(2C) + CO2 + H2O + Energy

NB. can be reversed, ie. glucose   glycogen

 Starch Breakdown / Digestion

Complex Dextrins Small Mono-

 Energy Sources

Instant
Blood sugar(glucose): ~1g/L or 20Cal or ~30mins.

Short Term
Liver/Muscles(glycogen): ~325g or ~6 hrs.

the more muscle, the more glycogen

any excess is converted into fat

Long Term
Fat(adipose tissue): ~ 20kg or ~35 days
 Nutritional / Dietary Carbohydrates

Starch - the digestible carbohydrate(for humans)

Simple - mono-/disaccharides, eg. sugars

Complex -seeds/roots of plants,
eg. grains(pasta), corn, potatoes, rice

Recommended - at least 55% of our Caloric intake

(10% sugar & 45% complex)
N A average - 20% sugar + 25% complex!
Cellulose - indigestible carbohydrate for humans

Soluble(pectins/gums) - fruits(apples), grain husks

(oat bran)
Insoluble(fiber/bulk/roughage) - potato skins, apple
peels, celery, lettuce

Recommended - ~30g/day
NA average - ~15g/day
 What is Dextrose?

Dextrose (Blood sugar) is the form of

glucose that rotates the plane of polarized
light in a clockwise direction.
 What is “invert sugar?”

• Hydrolysis of (+)sucrose (table sugar) produces equal

amounts of (+)glucose and (-) fructose (levulose).
• But, fructose optical rotation is larger (negatively) than
glucose rotation is positively. Hence, the resulting solution
is levorotatory (-).
• Thus, start with only (+) then get (-) after hydrolysis-so the
net result of hydrolysis is inversion of the direction of the
optical rotation
• Honey is mostly invert sugar –ie an equal mixture of
glucose and fructose
Sucrose -> Glucose + Fructose (Invert)
OH O
sucrose(+66)
HO
OH

HO HO
HO OH
O
sucrase

(invertase) HO
O

D-glucose(+52) D-fructose(-92)
+
 Maltose – the basic unit of Starch

OH O
(down) - linkage
HO

HO HO
OH O
O

OH
HO OH
requires maltase
(humans > yes)
 Cellobiose – the basic unit of Cellulose

(up) - linkage

OH O
HO
O
OH
O
HO HO
OH
HO HO

requires
cellobiase
(humans > no)
Why Dietary Fibre? It's Indigestible!
Beneficial statistical correlations for colon cancer,
obesity, diabetes, heart disease.
Acts as a sponge for water and other substances
Functions as a physical 'cleaner'
Soluble - can help lower cholesterol levels
reduces rate of glucose absorption
Insoluble - fills you up eat less fat
'cleans' folds in intestinal walls
no physical damage to intestinal walls
adsorbs/removes many 'nasties'
 Human Exploitation of Cellulose
Cellulose is a major component of grass, leaves,
wood, cotton(produced by photosynthesis).
World Biomass Production = 1011 tons annually

Present: Humans benefit indirectly by allowing

ruminants(cows, sheep) to digest cellulose
and convert it into protein which we eat.
Enzyme & Substrate: like a Lock & Key

Enzymes are huge protein molecules with intricate

but well-defined shapes. They are the catalysts that
bring about all the chemical reactions in our bodies.
For effective reactivity the molecule must fit into the
convolutions of the shape of the enzyme.
Much like a key must fit the tumblers of a lock.
 Lactose Intolerance
Lactase is the enzyme that specifically breaks the
-1,4- linkage of lactose to produce D-galactose and
D-glucose. Infants have a highly active form but
70% of adults have some lactase deficiency.
If lactose is not cleaved in small intestine it passes to
the colon and 1) absorbs water or 2) is degraded by
bacteria, resulting in cramps, diarrhea, etc.
About 10% of NA adults permanently lose their
lactase compared to 3% of Danes and 97% of Thais.
 Lactose (milk sugar) – a disaccharide

OH lactase + H2O
OH O

O
OH
O
HO HO
OH
HO HO
D-galactose
D-glucose

4-O-(-D-galactopyranosyl)-D-glucopyranose
 Solving the problem
• Buy it!
 Sweetness Index
Substance Relative Sweet Taste
Lactose 0.16
Maltose 0.33
Glucose 0.74
Sucrose 1.00
Fructose 1.73
(NB. Glucose + Fructose = Honey or Invert Sugar)
Aspartame 180
Saccharin 300
 Sucrose : lots of –OH’s: high
water solubility

-D-glucopyranosyl- -D-fructofuranoside
 Refined Sugar
NA sugar consumption: ~1kg (1750)
(annually/person) ~50
kg(1990)
Per day: 50, 000/365= 136 grams per person/day

world-wide production = >80 million tons

Dangers:
· dumps (60% fromglucose
too much cane; 40%
into from
bloodbeets)
too quickly
· all other nutrients(vitamins, minerals) are removed
Everybody’s Comfort Food !
Wow !
An Informative Label ?! …..Not Likely
Refined Sugar in some Processed Foods

Food % Sugar
Jello ~83
Coffeemate
~65 Shake’N Bake
~50 Salad Dressing
~30 Ketchup
~29 Ice cream
~21 Peaches(in syrup)
~18 Peanut butter
~9 Coca Cola
~9
 Sugar in human blood
• Blood sugar is glucose (dextrose)
• It is the only fuel for the brain and the
Central nervous system (CNS) and supplies
the E for basal metabolism
• For continuous supply, a concentration of
0.06 to 0.11 weight % is maintained
Control of Blood Sugar (normal ~100mg/dL)

Too Low
(<75mg/dL) = hypoglycemia(fainting)

Too High
(>150mg/dL) = hyperglycemia/diabetes
 Urine test for diabetes
• Above 0.16 weight % in blood , glucose
seeps through the kidneys into the urine
 Diabetes Mellitus
Type I (insulin dependent): ~10% of all diabetics
(juvenile onset)
Type II (non-insulin dependent; insulin receptors in
cells have become inactivated by excess use of
sugar): ~90% of all diabetics (formerly
called adult onset but now found in 10-12
year olds!)
NB. Diabetes is:
1) second only to trauma for leg amputation
2) leading cause of blindness in adults over 20
3) leading cause of kidney failure
4) almost triples risk of heart attack or stroke
 Type 1 Diabetes
• Body produces virtually no insulin
• Thus insulin needed for treatment
• Absence of insulin causes uncontrolled
lipolysis of fat and severe wasting of body
tissues, eventually resulting in death
 Living with Type 2 Diabetes
• Body makes too little insulin or its effect is
resisted
• In some cases insulin is needed
• sometimes controlled with a reduced sugar
diet
• Loss of weight will cause an increase in the
number of insulin receptors, hence
improved condition
 Canadians Discover Insulin (1921)

• Frederick Banting and his assistant Charles Best isolated

insulin from the pancreas of dogs (canine insulin) and
administered it to Type 1 patients
• Nobel Prize awarded to Banting and McLeod for this work
 Structural Differences
• Porcine & canine insulin are identical and
have 50/51 amino acids in common with
human insulin
• Bovine insulin and human insulin have
48/51 amino acids in common
• Thus porcine insulin most often used
 Source of Human Insulin

• Patients who are allergic to these can now

get cloned Insulin marketed as the Drug
Humulin
 Synthesis of Human Insulin
• Saran Narang (NRC Ottawa) 1930-2007
• Synthesised the proinsulin gene
• Enabled mass production of Humulin
• Via recombinant DNA
• Insulin is a protein
• 51 amino acids
• DNA>RNA>protein
Other molecules with sugar type
structures
 Fake Fats
• Simplesse - from egg white or milk proteins
· Emulsified starch - in Hellman’s light
mayonaisse · Emulsified protein - gelatin +
water · Olestra* ($200 million, by
Proctor&Gamble) - cramps/diarrhea(dehydration)
may cause
reduces absorption of vit. A, D, E,
K (fat- soluble
vitamins) into body
* not digested; available in USA since 1996;
must carry warning label; not legal in Canada
 Olestra = Sucrose Octa Palmitate

OH O
HO
OH

HO HO
HO OH
O

HO
O
Not OH but OR (R = O=C-C16 (sat. = palmitate)

NB. At least 6OHs esterified to be non-metabolized

Olestra – Indigestible !

Olestra a Triglyceride
 Chitin (an exoskeleton polymer)
OH O
HO
(D)-glucosamine
NH2 OH
HO

OH O
* O
OH O
O
HO
NH
O n*
O HO NH
CH3 O
CH3
 Glucosamine
• A simple amino sugar C6H13NO5.
• Produced commercially by hydrolysis of
crustacean exoskeletons
• Used in treatment of osteoarthritis
• Sold as a salt-either HCl or sulfate
• Typical dose up to 1.5gr/day
Glucosamine (3-aminoglucose)
 Blood Typing by Glycoprotein Antigens

Type A:
acetylgalactosamine-galactose-
acetylglucosamine-PRO fucose

Type B: lactose-galactose-acetylglucosamine-PRO
fucose

Type O: galactose-acetylglucosamine-PRO
fucose
 Chocolate - Covered Cherries

Cherries are first coated with

sugar paste(sucrose) +
sucrase(enzyme). After
hardening they are dipped in
chocolate and stored. After 1-
2 weeks the sucrose is
hydrolyzed/split by the
sucrase into glucose +
fructose which dissolves
easily in the cherry juice.

Chemistry is Everywhere !
 3 Cherry Blossom Questions
• One ingredient is called “invertase” .What
is another name for this?
• Another ingredient is soy lecithin. What
function does it serve?
• Another ingredient is “modified vegetable
oil” How has it been modified?
 Problem set #3
• Chapt 13 #1
• Chapt 15#1,8,9,10,11,25,29
• Chapt 16#1,9,11,12,18