Carbohydrates Lecture Bio024
Carbohydrates Lecture Bio024
OUTLINE
I. Carbohydrate: Introduction
II. Classification of Carbohydrates
A. Monosaccharide
B. Disaccharide
C. Oligosaccharide
D. Polysaccharide
III. Understanding Principles on the Molecular Structures of
Carbohydrates
A. Mirror Images
i. Two forms of “handedness”
a) “Left-handed” form
b) “Right-handed” form
ii. Two Classes of Objects Divided of their Mirror
Images
a) Superimposable Mirror Images
b) Nonsuperimposable Mirror Images
B. Chirality
i. Requirement to have a “chiral” molecule
ii. Importance of Chirality
C. Stereoisomerism: Enantiomers and Diastereomers ● Plants have two main uses for the carbohydrates they
i. Enantiomers
ii. Diastereomers
produce.
D. Designating Handedness (D,L) USing Fischer Projection
Formulas
E. Structures and Classification of Monosaccharide
F. Important Saccharide
IV. Cyclic Monosaccharide: Haworth Projection Formula
A. Haworth Projection Formula Rules
V. Biochemically Important Monosaccharides
VI. Reactions of Monosaccharide
A. Oxidation to Produce Acidic Sugars
B. Reduction to Produce Sugar Alcohols
C. Glycoside Formation
D. Phosphate Ester Formation
E. Amino Sugar Formation
VI. Disaccharides
A. Tabulation of Disaccharide
VII. Oligosaccharides
A. Importance of Oligosaccharides
VIII. Polysaccharides
A. Storage Polysaccharide
B. Structural Polysaccharide
C. Acidic Polysaccharide
i. Hyaluronic Acid
ii. Heparin
○ In the form of cellulose: carbohydrates serve as
D. Special Group
i. Glycosaminoglycans (GAGS) structural elements
ii. Proteoglycan Structure ○ In the form of starch: they provide energy reserves for
E. Other Natural Polysaccharide of Interest the plants
IX. Carbohydrate Related Diseases ● Dietary intake of plant materials is the major carbohydrate
A. Diabetes source for humans and animals.
B. Galactosemia ○ The average human diet should be ideally be about
two-thirds carbohydrate by mass
INTRODUCTION Carbohydrates have the following functions in humans:
● Carbohydrates are the most abundant class of 1. Carbohydrate oxidation provides energy; through
bioorganic molecules on planet earth. oxidation process
○ Although thor abundance in the human body is relatively 2. Carbohydrate storage, in the form of glycogen, provides
low, carbohydrates constitute about 75% by mass of dry a short-term energy reserve
plant materials. 3. Carbohydrate supply carbon atoms for the synthesis of
○ Green (chlorophyll-containing) plants produce other biochemical substances (proteins, lipids, and
carbohydrates via photosynthesis. nucleic acids)
■ In this process, carbon dioxide from the air and water 4. Carbohydrates form part of the structural framework of
from the soil are the reactants, and sunlight DNA and RNA molecules
absorbed by chlorophyll is the energy source 5. Carbohydrates linked to lipids are structural
components of cell membranes
MIRROR IMAGES
CLASSIFICATION OF CARBOHYDRATES
Monosaccharide ● Contains a single polyhydroxy
aldehyde or polyhydroxy ketone unit
● Can’t be broken down into simpler units
● Sugars with one molecule
● Naturally occurring monosaccharides
have from three to seven carbon atoms;
five– and six– carbon species are
especially common ● First, an important property of many molecules, including most
● Pure monosaccharides are water soluble, carbohydrates, is “handedness”, which is a form of
white, crystalline solids isomerism
● Cannot be hydrolyze further ○ Molecules that possess “handedness” exist in two forms:
● Considered as the building block of ■ “Left-handed” form
carbohydrates ■ “Right-handed” form
↪ These two forms are related to each other in the
Examples: Glucose, Fructose same way that a pair of hands is related to each
Disaccharide ● Contains two monosaccharide units other.
● covalently bonded to each other ↪ The relationship is that of mirror images
● Sugars that contain two monosaccharide ↪ A left hand and a right hand are mirror images of
units covalently bonded to each other each other.
● Crystalline, water-soluble substances ● Objects can be divided into two classes on the basis of
● Hydrolysis of a disaccharide produces two their mirror images:
monosaccharide units objects with ● Superimposable mirror images
superimposable are images that coincide at all
Sucrose (Table sugar) mirror images points when the images are laid
Lactose (milk sugar) (Achiral) upon each other.
Galactose
Oligosaccharide ● Contains three to ten monosaccharide
units covalently bonded to each other objects with ● Nonsuperimposable mirror
● Sugars that contains 3 to 10 nonsuperimposable images are images where not all
monosaccharide unit mirror images. points coincide when the images
(Chiral) are laid upon each other.
Tri, tetra, hexasaccharide
CHIRALITY
Raffinose
Diastereomers ● Are stereoisomers whose ● Enantiomers are said to be optically active because of the
molecules are not mirror way they interact with plane-polarized light.
images of each other. ○ Optically active compound: is a compound that rotates
● Cis-trans isomers (of both the the plane of polatized plane
alkene and the cycloalkane ■ Dextrorotatory (+) compound: is a chiral
types) are diastereomers compound that rotates the plane of polarized light in
Molecules that contain more than one chiral center can also a clockwise direction (means to the right, the Latin
exist in diastereomeric as well as enantiomeric forms. dextro means right)
- Substance rotates polarized to the right
(d-glucose; (+)-glucose)
■ Levorotatory compound: is a chiral compound that
rotates the plane of polarized light in a
counterclockwise (to the left the Latin Levo means
“left”) directions
- Substance rotates polarized light to the left
(l-glucose;(-)-glucose)
IMPORTANT SACCHARIDE
Sugar Where Found Biochemical Importance
D-Ribose Nucleic acids Structural elements of nucleic acids
(DNA & RNA (β-dribose and and coenzymes eg, ATP, NAD, NADP,
sugar, ATP β-ddeoxyribose) and
flavoproteins. Ribose phosphates are
sugar) ATP intermediates in pentose phosphate
pathway (PPP)
D-Ribulose Formed in metabolic Ribulose phosphate is an
processes intermediate in pentose phosphate
pathway (PPP)
D-Arabinose Gum arabic. Plum Constituent of glycoproteins
This table shows the possible number of optical isomer that the and cherry gums
sugar (aldoses or ketoses) structures can be made based on the
D-Xylose Wood gums, Constituent of glycoproteins
number of chiral centers/carbons and the location of the hydroxyl (aka wood proteoglycans,
(-OH) group in the each of the chiral centers/ccarbons. The higher sugar) glycosaminoglycans
the number of chiral center/carbon, the higher the possible number D-Lyxose Heart cells.muscle A constituent of a lyxoflavin isolated
of optical isomer from human heart
Carbon Chiral Optical Isomers Ruling (Location of –OH in the chiral L-Xylulose Intermediate in Found in urine in essential pentosuria
atoms carbons 2n centers) uronic acid pathway
(4)
Aldohexose 4 2 = 16, 8 D & 8 L ● 1st chiral carbon
(6c) OH alternating right and left Sugar Source Importance Clinical Significance
Aldopentose 3 2(3) = 8, 4 D & 4 L ● 2nd chiral carbon D-Glucose Fruit juices. “Sugar” of the body Present in the urine
(5c) OH alternating 2 rights and 2 lefts (Grape Hydrolysis of since blood contains (glycosuria) in diabetes
● 3rd chiral carbon sugar, starch, can dissolved glucose. mellitus owing to raised
Aldotetrose 2 2(2) = 4, 2 D & 2 L
OH alternating 4 rights and 4 lefts dextrose, sugar, maltose, Normal glucose level blood glucose
(4c)
● 4th chiral carbon blood sugar) and lactose 70-100mg/dL (hyperglycemia)
Ketohexose 3 2(3) = 8, 4 D & 4 L OH alternating 8 rights and 8 left
(6c)
Primary source of cell’s
Ketopentose 2 2(2) = 4, 2 D & 2 L energy
(5c)
D-Fructose Fruit juices. Can be changed to Hereditary fructose
(levulose, Present in glucose in the liver and intolerance leads to fructose
fruit sugar, Honey in equal so used in the body. accumulation and
THE 16 OPTICAL ISOMER OF ALDOHEXOSES dietary amount with Sweetest tasting sugar. hypoglycemia
sugar) glucose Dietary sugar because
less is needed for the
same amount of
sweetness
D-Galactose Hydrolysis of - Can be changed to Failure to metabolize leads
(brain sugar) lactose glucose in the liver to galactosemia and cataract
(just (disaccharide and metabolized
remember consisting of a - As brain sugar it is a
that our glucose and a constituent of
brain is a galactose nit) glycolipids and
galaxy of since this sugar glycoproteins found
information) does not occur in brain and nerve
free in nature. tissue
Synthesized in - D-galactose is
the mammary present in chemical
gland to make markers that
the lactose of distinguish various
Epimers - carbohydrates which vary in one position for the milk types of blood — A,
placement of the –OH group. The best examples are for D-glucose B, AB, and O
and D-galactose D-Mannose H/ydrolysis of A constituent of many Used for preventing urinary
plant mannans glycoproteins tract infections (UTIs) and
and gums treating
carbohydrate-deficient
glycoprotein syndrome, an
inherited metabolic disorder
CYCLIC MONOSACCHARIDE: HAWORTH PROJECTION ■ b-stereoisomer has the -OH group on the
FORMULA same side of the ring as the -CH2OH group
● Fischer projection formulas are useful for describing the
stereochemistry of sugars, but their long bonds and
right-angle bends do not give a realistic picture of the bonding
situation in the cyclic forms, nor do they accurately represent
the overall shape of the molecules
● Haworth projection formulas are more useful for those
purposes
○ Haworth projection formula is a two-dimensional
structural notation that specifies the three-dimensional
structure of a cyclic form of a monosaccharide.
○ The cyclic forms of monosaccharides result from the
ability of their carbonyl group to react intramolecularly
with a hydroxyl group. Structurally, the resulting cyclic D or L isomer: position of CH2OH group on the highest carbo
compounds are cyclic hemiacetals or hemiketals atom C5
● Pyranose (only aldohexose is capable): A cyclic
monosaccharide containing a six-atom ring
● Furanose (aldopentose and ketohexose are capable of
forming): five-atom ring
Because their ring structures resemble the ring structures in the
cyclic ethers pyran and furan, respectively
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDE
REACTIONS OF MONOSACCHARIDE
Five important reactions of monosaccharides are oxidation to
acidic sugars, reduction to sugar alcohols, glycoside formation,
phosphate ester formation, and amino sugar formation.Remember,
Sugar Where Can Be Found Biochemical Importance however, that other aldoses, as well as ketoses, undergo similar
D-Ribose (DNA nucleic acids (β-d-ribose Structural elements of nucleic reactions
and RNA Sugar, and β-d-deoxyribose) and acids and coenzymes, eg, ATP,
ATP Sugar) ATP NAD, NADP, flavoproteins.
Ribose phosphates are
intermediates in pathway (PPP)
Oxidation to Produce Acidic Sugars
The redox chemistry of monosaccharides is closely linked to
that of the alcohol and aldehyde functional groups
D-Ribulose Formed in metabolic Ribulose phosphate is an
processes intermediate in pentose
phosphate pathway (PPP)
D-Arabinose Gum arabic. Plum and Constituent of glycoproteins
cherry gums
D-Xylose (aka Wood gums, Constituent of glycoproteins
wood sugar) proteoglycans,
glycosaminoglycans
D-Lyxose Heart cells/muscle A constituent of a lyxoflavin
isolated from human heart
muscle
ACIDIC SUGARS
L-Xylulose Intermediate in uronic acid Found in urine in essential
pathway pentosuria Aldonic Acid - Acid group on top
- Uses weak oxidizing agent
Sugar Where Can Be Biochemical Clinical Significance
Found Importance
D-Glucose Fruit juices. Hydrolysis Sugar” of the body Present in the urine
(Grape of starch, cane sugar, since blood contains (glycosuria) in diabetes
Sugar, maltose, and lactose. dissolved glucose. mellitus owing to
dextrose, Normal glucose level raised blood glucose
blood sugar) 70-100mg/dL Primary (hyperglycemia
source of cell’s
energy.
D-Fructose Fruit juices. Present in Can be changed to Hereditary fructose
(levulose, Honey in equal glucose in the liver Intolerance leads to
Fruit sugar, amount w/ glucose and so used in the fructose accumulation
dietary body. Sweetest and hypoglycemia.
sugar) tasting sugar. Dietary
sugar because less
is needed for the
same amount of Alduronic Acid - Acid group on bottom
sweetness - Uses enzymes
● Glycosidic linkage: The bond that links the two TABULATION OF DISACCHARIDE
monosaccharides of disaccharide (glycoside) together
Features Maltose Cellobiose Lactose Sucrose
○ Glycosidic linkage is the bond in a disaccharide resulting Common Malt sugar Cellobiose Milk Sugar Table Sugar
from the reaction between the hemiacetal carbon atom names (⅓ as sweet as
-OH group of one monosaccharide and an -OH group of sucrose)
the other monosaccharide. Source Digestion by Intermediate in Milk. Juice of sugarcane
○ It is always a carbon-oxygen-carbon bond in a amylase or the hydrolysis of (20% by mass) &
hydrolysis of polysaccharide Clinical sugar beets (17%
disaccharide. starch. cellulose significance: in by mass)
Germinating lactase
cereals and malt Nursing deficiency, Clinical
mother=7-8% malabsorption significance: in
Cows milk=4-5%
leads to diarrhea sucrase deficiency,
and flatulence. malabsorption
Hence, lactose leads to diarrhea
intolerance and flatulence
Structural 2 Glucose units 2 Glucose units -β-D-galactose -α-D glucose &
Units -α-D glucose -β-D-glucose & & -D-glucose -β-D-fructose
& -D- glucose
- D-glucose
Glycosidic α (1-4)(head to β(1-4)(head to β(1-4)(head to α,β(1-2)(head to
linkage tail) tail) tail) head)
● It was noted that a cyclic monosaccharide contains a Enzymes Maltase Cellobiase Lactase Sucrase
hemiacetal (anomeric) carbon atom. Many disaccharides for
contain both a hemiacetal carbon atom and an acetal carbon hydrolysis
atom, as is the case for the precending disaccharide structure.
● Hemiacetal and acetal locations within disaccharides play an Maltose
important role in the chemistry of these substances - Malt sugar, one-third as sweet as sucrose, is produced
whenever the polysaccharide starch breaks down, as
happens in plants when seeds germinate and in human
beings during starch digestion
- It is a common ingredient in baby foods and is found in malted
milk. Malt (germinated barley that has been baked and
ground) contains maltose
- An interesting compound because of its use in alcohol
production (fermentation)
Cellobiose
- Like maltose, cellobiose contains two D-glucose
monosaccharide units. It differs from maltose in that one of
the D-glucose units—the one functioning as
hemiacetal—must have a or b configuration instead of the
a-configuration for maltose. This change in configuration
Lactose
- Milk sugar major sugar found in milk
- Uses:
- Ingredient in infant formulas that are designed to
stimulate mother’s milk
- Lactose as an excipient used as a filler or filler-binder
- Cost-effectiveness
- Availability
- Bland taste
- Low hygroscopicity
- Compatibility with active ingredients and other
excipients
- Excellent physical and chemical stability
- Water solubility
- Conditions associated with Lactose
1. Lactase persistence - used to describe the
condition where milk– drinking ability continues to
adulthood
2. Lactose intolerance – a condition in which people Tetrasaccharide Composed of:
lack the enzyme lactase, which is needed to Stachyose - α-D-galactose
hydrolyze lactose to galactose and glucose - α-D-galactose
Causes - α-D-glucose
- Genetic defect
- β-D-fructose
- Physiological decline w age
- Injury to the mucosal lining of the
intestines
3. Galactosemia – caused by the absence of one or
more of the enzymes needed for the conversion of
galactose to glucose
- In people with this condition, galactose and its
toxic metabolic derivative galactitol (dulcitol)
accumulate in the blood
- Can cause mental retardation in infants and
even death
Sucrose
- Composed of a-D-glucose and b-D-fructose
- Table sugar, is the most abundant of all disaccharides and
occurs throughout the plant kingdom
- The glycosidic linkage is not a (1:4) linkage, as was the case
for maltose, cellobiose, and lactose. It is instead an a b(1:2)
glycosidic linkage
- The –OH group on carbon 2 of D-fructose (the hemiacetal
carbon) reacts with the -OH group of carbon 1 of D-glucose
(the hemiacetal carbon)
OLIGOSACCHARIDES
● Are saccharides that contain three to tn monosaccharides
units bonded to each other via glycosidic linkages. IMPORTANCE OF OLIGOSACCHARIDE
○ Two naturally occurring oligosaccharides found in ● The type of blood a person has (O, A, B, or AB) is determined
onions, cabbage, broccoli, brussel sprouts, whole wheat, by the type of oligosaccharide that is attached to the person’s
and all types of beans are the trisaccharide raffinose and red blood cells
the tetrasaccharide stachyose. ● Four monosaccharides contribute to the make-up of the
Trisaccharide Composed of: oligosaccharide “marking system”
Raffinose - α-D-galactose
- α-D-glucose
- β-D-fructose
TYPES OF POLYSACCHARIDES
a. STORAGE POLYSACCHARIDE
- Used as an energy source in cells
Examples: start and glycogen
STARCH GLYCOGEN
Energy storage polysaccharide in plants Energy storage polysaccharide
for animals aka animal starch.
A homopolysaccharide containing only
glucose monosaccharide units Branched polysaccharide
containing only glucose units.
amylum
Liver cells and muscle cells are
the storage sites for glycogen in
humans
Amylose Amylopectin 3x more highly branched than
- straight-chain - A branched glucose amylopectin and it is much
glucose polymer, polymer, accounts larger, with up to 1,000,000
usually accounts for the remaining glucose units present
for 15%-20% of 80%-85% of the
the starch starch
- With 300-500 - More water soluble
monor units of because of increase
glucose in branching
- Contains 100,000
glucose units
Glucose units are connected by a(1:4) The two opposing processes are
glycosidic linkages called glycogenesis and
glycogenolysis, the formation and
Both a(1:4) and (1:6) decomposition of glycogen,
respectively
b. STRUCTURAL POLYSACCHARIDE
- Serves as a structural element in plant cell walls and
animal exoskeletons like chitin and cellulose
Cellulose Chitin
Gossypium hirsatum
proteoglycan [proteoglycans = ○ found primarily in the cornea of the eye and in joint
Glycosaminoglycans + proteins] cartilage for mechanical support and structural role
○ are more carbohydrate than protein, hence their ○ structural polysaccharide in nails
properties are mainly determined by the ● Dermatan sulfate
carbohydrate portion of the molecule. ○ closely related GAG, which is composed of glucuronic
○ The carbohydrate moieties may contain acid and N-acetylgalactosamine
carboxylic acids or sulfated sugars thus the GAG ○ structural polysaccharide in skin
chain carry negative charge
1. Type 1
- most diagnosed in children and teenagers. It’s an
autoimmune condition.
- When you have type 1 diabetes, your immune
system attacks the cells in your pancreas
responsible for making insulin.
- Body doesn't produce enough insulin
- The result of inadequate insulin production by the
beta cells of the pancreas
- Control of this situation involves insulin injections
and special dietary programs
2. Type 2
- happens when your body stops responding to the
insulin your pancreas makes. Over time, your
pancreas also stops producing enough insulin. It’s 1. Brain damage
generally linked to a combination of genetic and 2. Cataracts
lifestyle factors. 3. Jaundice
- Body produces insulin but can’t use it well 4. Enlarged liver
- Results from insulin resistance, a condition in which 5. Kidney damage
cells fail to use insulin properly. Bodily insulin
production may be normal, but the cells do not If a galactosemic infant is given milk, unmetabolized milk sugars
respond to it normally. build up and damage the liver, eyes, kidneys and brain
- Treatment involves use of medications that
decrease glucose production and/or increase insulin How is Galactosemia Treated?
levels, as well as carefully regulated diet to Treatment requires the strict exclusion of lactose/galactose from
decrease obesity if the latter is a problem, the diet. A person with galactosemia will never be able to properly
- More efficient use of undamaged insulin receptors digest foods containing galactose. There is no chemical or drug
occurs at increased insulin levels substitute for the missing enzyme at this time. An infant
3. Gestational diagnosed with galactosemia will simply be changed to a formula
- This type of diabetes is a response to the hormonal that does not contain galactose. With care and continuing medical
changes that happen during pregnancy. The advances, most children with galactosemia can now live normal
hormones made in the placenta can lower your lives
body’s sensitivity to insulin. This may result in high
blood sugar during pregnancy
- A temporary condition in pregnancy
1. What are the negative effects of carbohydrates?
Refined carbs may increase blood triglycerides, blood
There isn’t a cure yet for diabetes, but losing weight, eating
sugar levels and cause insulin resistance. All of these are
healthy food, and being active can really help. Taking medicine as
major risk factors for heart disease and type 2 diabetes.
needed, getting diabetes self-management education and support,
2. How can carbohydrates lead to diabetes?
and keeping health care appointments can also reduce the impact
When a person consumes carbohydrates, the digestive
of diabetes on your life.
system breaks some of them down into glucose. This
glucose enters the blood and raises blood sugar, or
2. GALACTOSEMIA glucose, levels. When blood glucose levels rise, beta cells
- Also known as: in the pancreas release insulin. Insulin is a hormone that
○ galactose-1-phosphate uridylyl makes our cells absorb blood sugar for energy or storage.
○ transferase deficiency As the cells absorb the blood sugar, blood sugar levels
○ transferase deficiency galactosemia start to drop. When blood sugar levels drop below a
○ GALT deficiency certain point, alpha cells in the pancreas release
REFERENCES