Biochemistry Midterm

CARBOHYDRATES
• Carbohydrates are the most abundant class of biological
molecules.
• Structure (cell walls, connective tissue).
• Important for cell signalling and cell-cell interactions.

CLASSIFICATIONS:
• MONOSACCHARIDES – Glucose, fructose
• OLIGOSACCHARIDES
➢ Disaccharides, trisaccharides, tetrasaccharides,
pentasaccharides, hexasaccharides, (up to 10
monosaccharides).
• POLYSACCHARIDES
➢ Homopolysaccharides – starch, glycogen, cellulose,
chitin, inulin.
➢ Heteropolysaccharides
➢ Complex carbohydrates

Classification of Monosaccharides:
▪ ALDOSES – Glyceraldehdye(trioses),
Erythrose(tetroses), Ribose(Pentoses), Glucose(Hexoses)
 ▪ KETOSES – Dihydroxyacetone(3), Erythrulose(4),
Ribulose(5), Fructose(6), Sedoheptulose(Heptoses 7)

Aldoses are monosaccharides with an aldehyde group with

many hydroxyl (-OH) groups. O = C – H

Ketoses are monosaccharides with a ketone group with many

hydroxyl (-OH) groups. CH2OH – C = O

EPIMERS
Two sugars that only differ in the configuration around one
carbon atom.

Monosaccharides have asymmetric centers.

Ex. Two stereoisomers of Glyceraldehyde

1. Ball-and-stick models
2. Fisher projection formulas
3. Perspective formulas

Other stereoisomers have unique names, e.g., glucose,

mannose, galactose, etc.

D-glucose – found on the 2nd to the last line. The OH is on

the left side.

L-glucose – found on the 2nd to the last line. The OH is on the

right side.
CYCLIC STRUCTURES
Are the prevalent form of monosaccharides with 5 or 6
carbon atoms.

Alpha anomers – the OH is below.

Beta anomers – the OH is above.

ANOMERS

Isomers form of monosaccharides that differ only in the

configuration of 1 carbon atom.

MUTAROTATION PROCESS

The a and b anomers of D-glucose interconvert in aqueous

solution.

REDUCING SUGARS

▪ Sugars that contain aldehyde groups that are oxidized to

carboxylic acids.
▪ Common test reagents are:
- Benedicts reagent (CuSO4 / citrate)
- Fehlings reagent (CuSO4 / tartrate)
• They are classified as reducing sugars since they reduce
the Cu2+ to Cu+ which forms as a red precipitate,
copper(i) oxide.
SUCROSE is non reducing sugar.
DISACCHARIDES:
Maltose – a cleavage product of the hydrolysis of starch.
Lactose – milk sugar, composed of galactose & glucose.
Sucrose – common table sugar, has a glycosidic bond
linking the anomeric hydroxyls of glucose & fructose.

Disaccharides consists of two monosaccharides.

Glucose + Glucose = Maltose + H2O.Also known as malt sugar.

Glucose + Galactose = Lactose + H2O.

Glucose + Fructose = Sucrose + H2O. Obtain from sugar

canes and sugar beets.

Disaccharides contain a glycosidic bond.

Glycosidic bond protects the anomeric carbon from oxidation.

ISOMALTOSE – Enzymic hydrolysis of starch.

LATULOSE – Heated milk, mainly synthetic.

TREHALOSE - Yeast and fungi; the main sugar of insect

hemolymph.
POLYSACCHARIDES also called GLYCANS
• Homopolysaccharides: (starch, glycogen, cellulose, chitin,
inulin).
• Heteropolysaccharides: (peptidoglycan, agarose,
hyaluronate, chondroitin sulfate, keratan sulfate,
heparin)
• Characteristics:
- MW from 200,000
- White and amorphous product (glassy)
- Not sweet
- Not reducing sugar
- Form colloidal solutions or suspensions
-

Most carbohydrates found in nature occur as polysaccharides.

STARCH – most common storage polysaccharides in plants.

Amylose and Amylopectin, the polysaccharides of starch.

AMYLOSE – linked by a-1,4 glycosidic bonds. A continuous

(unbranched) chain.

AMYLOPECTIN – has a bond between the glucose units. A

branched-chain polysaccharide. Has a-1,6 bonds to branches.

GLYCOGEN – also known as animal starch. Stored in muscle

and liver. Present in cell as granules. Complete hydrolysis
yields glucose.

DEXTRINS – are intermediates in the hydrolysis of starch.

CELLULOSE – a major constituent of plant cell walls, consists
of long linear chains of glucose with B(1 to 4) linkages.

o This promotes intra-chain and inter-chain H-bonds

and Van der Waals interactions, that cause cellulose
chains to be straight & rigid.
o Cannot be digested by human because human cannot
breakdown – B(1 to 4) glycosidic bonds.

CHITIN – exoskeleton of anthropods. Linear, unbranched

homopolymer. Only difference from cellulose is the acetylated
amino group instead of OH at C-2.

INULIN – polysaccharides of fructose, used to determine the

glomerular filtration rate.

GLYCOSAMINOGLYCANS = linear polymers composed of

repeating disaccharide units.

- Tend to be NEGATIVELY CHARGRED, because of

the prevalence of acidic groups.
- The constituent monosaccharides tend to be
MODIFIED, with acidic groups, amino groups, sulfate
hydroxyl and amino group, etc.
- HYALURONATE (hyaluronan) is a glycosaminoglycan.

HEPARIN & HEPARAN SULFATE – initially synthesized on

a membrane-embedded core protein as a polymer of
alternating N-acetylglucosamine (N-Ar) and Glucuronate
residues (GR). Later, in segment of the polymer, GR may be
converted to the sulfate sugar IDURONIC ACID, while N-aR
may be deacetylated and/or sulfated.

HEPARIN – a soluble found in granules of mast cells, has a

structure similar to that of heparan sulfate, but is more
HIGHLY SULFATED.

- When released into the blood, it inhibits clot

formation by interacting with the protein
antithrombin.
- Has an extended helical conformation.
- Charge repulsion
- Has 10 residues, alternating IDS (idunorate-2-
sulfate) & SGN (N-sulfo-glucosamine-6-sulfate).

COMPLEX CARBOHYDRATES
GLYCOCONJUGATES (Proteoglycans, Glycoproteins,
Glycolipids).

- Biologically active molecule made from a

carbohydrate covalently linked to a protein or lipid.
- Found at cell surfaces.

Both GLYCOPROTEINS and GLYCOLIPIDS are important in:

- Cell-Cell recognition and adhesion

- Cell migration and development
- Blood clotting, The immune response, Wound healing
The Carbohydrates parts serve as the information carrier by
providing specific, high affinity recognition sites.

PROTEOGLYCANS

- Some bind non-covalently to hyaluronate via protein

domains called LINK MODULES.

Ex. Aggrecan and Versican

- Some cell surface heparan sulfates

glycosaminoglycans remain covalently linked to core
proteins embedded in the plasma membrane.

GLYCOPROTEINS

- Found on the outer surface of plasma membrane, in

the extracellular matrix, in the blood, and in the
specific organelles.
- Increase polarity and solubility of the proteins.
- May influence the folding process
- Protect from proteolytic enzymes
- Responsible for biological activities

CARBOHYDRATE CHAINS of plasma membrane glycoproteins

and glycolipids usually face the OUTSIDE OF THE CELL.
LECTINS are glycoproteins that recognize and bind to
specific oligosaccharides.

Ex. Of plant lectins: Concanavalin A & wheat germ agglutinin.

GLYCOLIPIDS
- Blood group antigens are immunochemical markers
made of glycolipids on the surface of red blood cells.
- Those with type A cells have type A antigens.
- On their cell surfaces, B have B antigens, AB have
both, O carry the O antigen.

The only difference appears at the terminal sugar.

Type O blood – the universal blood.

DIGESTION, ABSORPTION, AND METABOLISM

DIGESTION

- Breakdown of food in body in preparation for

absorption.
- Mechanical digestion – Food broken into smaller
pieces by teeth and moved along gastrointestinal
tract by peristalsis.
 - Chemical digestion – Carbohydrates, proteins, and
fats broken down into nutrients that tissues can
absorb and use.

• Chemical changes occur through hydrolysis

• Enzyme act on food substances
- Causing them to break down into simple compounds
• Enzyme can act as catalyst
- Speeds up chemical reaction without itself being
changed in the process

DIGESTION IN THE MOUTH

▪ Teeth break up food
▪ Food mixed with saliva
- Forming bolus
▪ Salivary amylase act on starch
▪ Food in mouth for brief length of time

DIGESTION IN THE ESOPHAGUS

▪ Food travels through this muscular tube
- Connects mouth to stomach
▪ Peristalsis and gravity act to move bolus
▪ Cardiac sphincter opens to allow passage of bolus into
stomach

DIGESTION IN THE STOMACH

 ▪ Temporary storage of food
▪ Kneading and mixing of food with gastric juices
▪ Regulation of slow, controlled emptying of chyme into
intestine
▪ Destruction of most bacteria consumed
▪ Secretion of intrinsic factor for vitamin B12
▪ Gastric juices contain hydrochloric acid, pepsin, and
mucus
▪ In children, two additional enzymes: RENNIN &
GASTRIC LIPASE

DIGESTION IN THE SMALL INTESTINE

▪ Hormones released
- Secretin causes pancreas to release sodium
bicarbonate to neutralize acidity of chyme
- Cholecystokinin triggers gallbladder to release bile
▪ Bile
- Emulsifies fat after secreted into small intestine
- Produced in liver
- Stored in gallbladder

Enzymes found in pancreatic juice secreted into small

intestine

▪ Pancreatic proteases
- Splits proteins
- E.g., trypsin, chymotrypsin, carboxypeptidases
 ▪ Pancreatic amylase
- Convert starches (polysaccharides) to simple sugars

Enzymes found in pancreatic juice secreted into small

intestine

▪ Pancreatic intestine
- Reduces fats to fatty acids and glycerol
▪ Small intestine itself produces enzymes
- Lactase, maltase, and sucrase convert lactose,
maltose, and sucrose to simple sugars
- Peptidases reduce proteins to amino acids

Small intestine divided into three sections:

▪ Duodenum – First section

▪ Jejunum – Middle section
▪ Ileum – Last section

DIGESTION IN THE LARGE INTESTINE

▪ Consists of cecum, colon, and rectum
▪ Major tasks of cecum:
- Absorbs water and salts from undigested foods
- Kneads content for enhanced absorption
- Collects volatile fatty acids to be absorbed and used
as sources of energy
▪ Digested food progress through colon to anal canal

Contents travel through:

1. Ascending colon
 2. Transverse colon
3. Descending colon
4. Sigmoid colon
5. Rectum
6. Anal canal

ABSORPTION
• Passage of nutrients into blood or lymphatic system
• Nutrients must be in simplest form
- Carbohydrates – Simple sugars
- Proteins – Amino acids
- Fats – Fatty acids and glycerol

ABSORPTION IN THE SMALL INTESTINE

• Where most absorption occurs
• Villi
- Hairlike projections that increase surface area for
maximum absorption
- Absorb nutrients from chyme and transfer them to
bloodstream
• Water absorbed in stomach, small intestine, and large
intestine

ABSORPTION IN THE LARGE INTESTINE

• Mucus protects colon from digestive juices
• Major tasks of large intestine:
- Absorbs water
 - Synthesizes vitamin B and vitamin K
- Collects food residue
• Undigested food excreted as feces

METABOLISM
➢ Transformation of nutrients into energy within cell
➢ Occurs after digestion and absorption
- Nutrients carried by blood to cells of body
➢ Aerobic metabolism combines nutrients with oxygen
within each cell
- Also known as oxidation

Anaerobic metabolism reduces fats without use of oxygen.

Krebs cycle - Complete oxidation of carbohydrates, proteins,

and fats.

Anabolism - Process of using energy from oxidation to create

new compounds.

Catabolism – Breakdown of compounds during metabolism.

• Controlled primarily by hormones secreted by thyroid

gland
- Triiodothyronine (T3)
- Thyroxine (T4)

ENERGY

Needed for involuntary and voluntary activity

Involuntary activity
 - E.g., maintenance of body tissue, temperature, and
growth
Voluntary activity
- E.g., walking, swimming, eating, reading, typing

Three groups of nutrients provide energy:

1. Carbohydrates
2. Proteins
3. Fats

Carbohydrates should be primary source of energy.

Kilocalorie
- Unit used to measure energy value of foods
- Also known as calorie
Calorie
- Amount of heat needed to raise temperature of 1
kilogram (kg) of water 1 degree Celsius

o 1 gram (g) of carbohydrate yields 4 calories

o 1 g of protein yields 4 calories
o 1 g of fat yields 9 calories
o 1 g of alcohol yields 7 calories

BMR
Rate at which energy is needed for body maintenance
Energy necessary to carry on all involuntary vital
processes while body at rest
 Also known as resting energy expenditure (REE)

Affecting factors:
Lean body mass
Body size
Sex
Age
Heredity
Physical condition
Climate

Method used to estimate BMR:

- Convert body weight from pounds to kg
- Multiply kg by 24 (hours per day)
- Multiply answer by 0.9 for females and by 1.0 for
males.
o Food broken down through processes of mechanical and
chemical digestion into nutrients that can be absorbed.
o Enzymes break down nutrients.
o Absorption occurs mostly in small intestines.
o During metabolism, carbohydrates and proteins combine
with oxygen
- Oxidation
o Energy released during oxidation measured in calories
o Person’s energy requirement can be measured in part by
estimating BMR
 QUALITATIVE TEST FOR CARBOHYDRATES
❖ Carbohydrates are the key source of energy used by
living things.
❖ Also serve as extracellular structural elements as in
cell wall of bacteria and plant.
❖ Carbohydrates are defined as the polyhydroxy
aldehydes or polyhydroxy ketones.

Classifications:
o Simple sugar: (one unit)
- Monosaccharides contain one monosaccharide unit.
o Complex sugar (more than one):
- Disaccharides contain two monosaccharide units.
- Oligosaccharides contain 3-9 monosaccharide units.
- Polysaccharides can contain more than 9
monosaccharide units.

Complex carbohydrates can be broken down into

smaller sugar units through a process known as
hydrolysis.

Molisch test
 o This test is specific for all carbohydrates.
Monosaccharide gives a rapid positive test, Disaccharides
and polysaccharides react slower.

Objective: To identify the carbohydrate from other

macromolecules lipids and proteins.

o Positive reaction when producing violet ring between the

surface separations.

Benedict's test
o Benedict's reagent is used as a test for the presence of
reducing sugars.
o All monosaccharides are reducing sugars; they all have a
free reactive carbonyl group.
o Some disaccharides have exposed carbonyl groups and
are also reducing sugars. Other disaccharides such as
sucrose are non-reducing sugars and will not react with
Benedict's solution.
o Large polymers of glucose, such as starch, are not
reducing sugars.

Objective: To distinguish between the reducing and non-

reducing sugars.

Principle: The copper sulfate (CuSO4) present in Benedict's

solution reacts with electrons from the aldehyde or ketone
group of the reducing sugar in alkaline medium.
 o Reducing sugars are oxidized by the copper ion in solution
to form a carboxylic acid and a reddish precipitate of
copper oxide.
o A positive test is indicated by: The formation of a
reddish precipitate.

Barfoed’s Test
o This test is performed to distinguish between
monosaccharides and disaccharides/polysaccharides.

Objective: To distinguish between mono-, di- and poly

saccharides.

o Reducing monosaccharides are oxidized by the copper ion

in solution to form a carboxylic acid and a reddish
precipitate of copper (I) oxide within three minutes.
Reducing disaccharides undergo the same reaction, but
do so at a slower rate.
o The nonreducing sugars give negative result.
o Disacchride is a weaker reducing agent than
monosacchride, so monosacchride will reduce the copper
in less time.

Bial’s Test
 o This test is used to distinguish between pentose
and hexose monosaccharides.
Objective: To distinguish between pentose monosaccharide
and hexose monosaccharide

o The test reagent dehydrates pentoses to form

furfural. Furfural further reacts with orcinol and the
iron ion present in the test reagent to produce a bluish
or green product, while hexoses yield muddy-brown to
grey condensation product.

Seliwanoff's Test
o This test is used to distinguish between aldoses (like
glucose) and ketoses (like fructose).

Objective: To distinguish between aldose and ketone sucrose.

Principle: Seliwanoff's Test uses 6M HCl as dehydrating

agent and resoncinol as condensation reagent.

o Resorcinol present in the test reagent to produce a

cherry red product within two minutes.
o Aldohexoses react to form the same product, but do
so more slowly giving yellow to faint pink color.
o Cherry red color product = Positive Reaction and has
Fructose & Sucrose.