CHM369: Macromolecular Chesmistry I

Classification of macromolecules
What are macromolecule?
 Very large molecule,
 usually with a diameter ranging from about 100 - 10,000 angstroms per
molecule, any (10−5 to 10−3 mm)
 The molecule is the smallest unit of the substance that retains its characteristic
properties

The four major classes of molecules found in living things are giants in the
microscopic world:
• Carbohydrates,
• Proteins,
• Lipids And
• Nucleic Acids
What are macromolecule?

Each have different jobs that help keep organisms performing their life
functions
 Carbohydrates Store energy, provide fuel, and build structure in body,
main source of energy, structure of plant cell wall
 Protein: Provide structural support, transport, enzymes, movement,
defense
 Lipid: Insulator and stores fat and energy
 Nucleic acids: Stores and transfers info
 Carbohydrates
 Sources are numerous
 Based on number of sugar units present, can be classified as
• Monosaccharides- cannot be divided (hydrolyzed) further into
simpler forms
• Disaccharides - contains 2 molecules of same or different
monosaccharide and produces the molecules upon hydrolysis
• Oligosaccharides - contains 3-10 molecules of monosaccharide units
yielding same upon hydrolysis
• Polysaccharides - contained more than 10 molecules of same or
different monosaccharide units
 Can also be classified into
• Homopolysaccharides &
• Heteropolysaccharides
 Protein
 Fundamental building blocks of life
 Carry out many diverse functions in the cell
 Assembled from amino acids
 Sequence of amino acids known as the primary structure of a protein
 Interactions of individual amino acids in a protein cause the linear chain
to fold into the secondary structures
 Interactions of distant amino acids lead to further folding of the protein-
tertiary structure
 Assembly of multiple folded chains (subunits) is known as quaternary
protein structure
 The order of amino acids determines the primary structure
Protein
 Amino acids that are bound together in a chain are called polypeptides
 The amino acids are linked by their amino (–NH3) and carboxyl (–COOH)
groups which form peptide bonds.
 The chain of linked carbon and nitrogen atoms is the backbone of the protein
 The amino acid side chains sticking out perpendicularly
 The order of amino acid residues in the polypeptide chain is the primary
structure
 Hydrogen bonds among close amino acid residues contribute to the
secondary structure
 The amino and carboxyl groups of the protein backbone can form hydrogen
bonds
 When multiple amino acid residues in close proximity form hydrogen bonds,
local structures such as alpha-helices and beta-pleated sheets can form
Protein
 Interactions of distant side chains determine the tertiary structure
 The tertiary structure of a protein describes the 3-dimensional arrangement of a protein
 To stabilize a tertiary structure, amino acid residues interaction might be far apart
within the polypeptide chain
 The interactions can be weak and non-covalent (e.g., ionic bonds, hydrophobic
interactions or hydrogen bonds) or strong and covalent (e.g., disulphide bridges)
 All interactions contribute to the shape of the protein and its function
 Multiple polypeptide chains can form a single protein
 So far, we considered proteins that are created of a single polypeptide chain.
 Many proteins consist of subunits, that are each formed of one polypeptide chain
 The composition and interaction of multiple protein subunits are known as the
quaternary structure
Protein
 Lipids
Lipids, commonly referred to as fats, are predominantly composed of carbon
and hydrogen
This makes lipids hydrophobic (not water friendly) which implies they are not
soluble in water because by nature they are non-polar
Lipid molecules may also contain limited amounts of oxygen, nitrogen, sulfur,
and phosphorous
Lipids serve numerous and diverse purposes in the structure and functions of
organisms
They can be a source of nutrients, a storage form for carbon, energy-storage
molecules, structural components of membranes, and involved in chemical
signaling and communication
Lipids also provide insulation from the environment for plants and animals
For example, they help keep aquatic birds and mammals dry because of their
water-repelling nature
Lipids
 Lipids are also the building blocks of many hormones
 Lipids comprise a broad class of many chemically distinct compounds which
include; fats, oils, phospholipids, steroids and waxes
 Lipids, commonly referred to as fats, are predominantly composed of carbon
and hydrogen
 This makes lipids hydrophobic (not water friendly) which implies they are not
soluble in water because by nature they are non-polar
 May also contain limited amounts of oxygen, nitrogen, sulfur, and phosphorous
 Fats and Oils (also called triglycerides) are esters of fatty acids and glycerol
(propan-1, 2, 3-triol)
 Fats are obtained from saturated fatty acids while oils are obtained from
unsaturated fatty acids
 Fatty acids are lipids that contain long-chain hydrocarbons terminated with a
carboxylic acid functional group
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Lipids
The longer the hydrocarbon chain the greater the hydrophobicity (“water
hating”) or non-polar nature
The hydrocarbon chain length may vary from 10-30 carbons (most usual is 12-
18)
The non-polar hydrocarbon alkane chain is an important counter balance to the
polar acid functional group
In acids with only a few carbons, the acid functional group dominates and gives
the whole molecule a polar character
However, in fatty acids, the non-polar hydrocarbon chain gives the molecule a
non-polar character.
Fatty acids with hydrocarbon chains that contain only single bonds are
called saturated fatty acids because they have the greatest number of hydrogen
atoms possible and are, therefore, “saturated” with hydrogen
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Lipids
Saturated fatty acids have a straight, flexible carbon backbone, whereas
unsaturated fatty acids have “kinks” in their carbon skeleton because each
double bond causes a rigid bend of the carbon skeleton
These differences in saturated versus unsaturated fatty acid results in different
properties for the corresponding lipids in which the fatty acids are
incorporated
E.g., lipids containing saturated fatty acids are solids (fats) at room
temperature, whereas lipids containing unsaturated fatty acids are liquids
(oils)
Melting point principle: as the molecular weight increases, the melting point
increases. This is observed in the series lauric (C12), palmitic (C16), stearic
(C18).
At 25oC, Lauric acid which will melt at 44o is still a solid, while arachidonic
acid will melt at -50o is a liquid at room temperature 12
Lipids
Unsaturated fatty acids may be
Table 1: Common Fatty Acids converted to saturated fatty acids
Acid Name Structure Melting Point by the relatively simple
SATURATED hydrogenation reaction
CH3(CH2)10COOH
Vegetable oils are commonly
Lauric +44
referred to as “polyunsaturated”.
Palmitic CH3(CH2)14COOH +63
This simply means that there are
Stearic CH3(CH2)16COOH +70 several double bonds present.
UNSATURATED Vegetable oils may be converted
Oleic CH3(CH2)7CH=CH(CH2)7COOH +16 from liquids to solids by the
Linoleic CH3(CH2)4(CH=CHCH2)2(CH2)6COOH -5
hydrogenation reaction.
Margarines and shortenings are
Linolenic CH3CH2(CH=CHCH2)3(CH2)6COOH -11 “hardened” in this way to make
Arachidonic CH3(CH2)4(CH=CHCH2)4(CH2)2COOH -50 them solid or semi-solids.
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Lipids
Percent Fatty Acid Present in Triglycerides
Fat or Oil Saturated Unsaturated

Palmitic Stearic Oleic Linoleic Other

Animal Origin
Butter 29 9 27 4 31
Lard 30 18 41 6 5
Beef 32 25 38 3 2
Vegetable Origin
Corn oil 10 4 34 48 4
Soybean 7 3 25 56 9
Peanut 7 5 60 21 7
Olive 6 4 83 7 –

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Lipids
 Phospholipids (Phospholglycerides) are esters of only two fatty acids, phosphoric acid
and a trifunctional alcohol – glycerol
 The fatty acids are attached to the glycerol at the 1 and 2 positions on glycerol through
ester bonds
 There may be a variety of fatty acids, both saturated and unsaturated, in the phospholipids
 A phospholipid is amphiphilic having both hydrophobic and hydrophilic regions
 The fatty acid chains are hydrophobic and exclude themselves from water, whereas the
phosphate is hydrophilic and interacts with water
 Phospholipids are similar to the triglycerides with a couple of exceptions
 The third oxygen on glycerol is bonded to phosphoric acid through a phosphate ester
bond (oxygen-phosphorus double bond oxygen)
 In addition, there is usually a complex amino alcohol also attached to the phosphate
through a second phosphate ester bond.
 The complex amino alcohols include choline, ethanolamine, and the amino acid-serine
 The properties of a phospholipid are characterized by the properties of the fatty acid chain
and the phosphate/amino alcohol
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Lipids
 The phosphate group has a negatively charged oxygen and a positively charged nitrogen to
make this group ionic. In addition there are other oxygen of the ester groups, which make
on whole end of the molecule strongly ionic and polar
 Phospholipids are major components in the lipid bilayers of cell membranes
 There are two common phospholipids:
o Lecithin (contains the amino alcohol, choline) and
o Cephalins (contain the amino alcohols serine or ethanolamine)
 Lecithin: is probably the most common phospholipid, found in egg yolks, wheat germ, and
soybeans.
 Also extracted from soy beans for use as an emulsifying agent in foods
 Lecithin is an emulsifier because it has both polar and non-polar properties
 This enable it to cause the mixing of other fats and oils with water components
 Lecithin is also a major component in the lipid bilayers of cell membranes
 Lecithin contains the ammonium salt of choline joined to the phosphate by an ester linkage
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Lipids
 The nitrogen has a positive charge, just as in the ammonium ion. In choline, the nitrogen
has the positive charge and has four methyl groups attached.
 Cephalins: are phosphoglycerides that contain ehtanolamine or the amino acid serine
attached to the phosphate group through phosphate ester bonds
 A variety of fatty acids make up the rest of the molecule
 Cephalins are found in most cell membranes, particularly in brain tissues.
 They are also important in the blood clotting process as they are found in blood platelets

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Lipids
 Sex Hormones are also steroids.
 The primary male hormone, testosterone, is responsible for the development of
secondary sex characteristics.\
 Two female sex hormones, progesterone and estrogen or estradiol control the ovulation
cycle.
 Note that the male and female hormones have only slight differences in structures, but
yet have very different physiological effects.
 Testosterone promotes the normal development of male genital organs and is
synthesized from cholesterol in the testes
 It also promotes secondary male sexual characteristics such as deep voice, facial and
body hair.
 Estrogen, along with progesterone regulates changes occurring in the uterus and ovaries
known as the menstrual cycle.
 Estrogen is synthesized from testosterone by making the first ring aromatic which results
in mole double bonds, the loss of a methyl group and formation of an alcohol group 18
Lipids
 Steroids is major class of lipids, which have structures totally different from the other
classes of lipids.
 The main feature of steroids is the ring system of three cyclohexanes and one
cyclopentane in a fused ring system.
 There are a variety of functional groups that may be attached
 The main feature, as in all lipids, is the large number of carbon-hydrogens which make
steroids non-polar
 Steroids include well known compounds such as cholesterol, sex hormones, birth
control pills, cortisone, and anabolic steroids.
 Cholesterol is the best known and most abundant steroid in the body
 Cholesterol is formed in brain tissue, nerve tissue, and the blood stream
 It is the major compound found in gallstones and bile salts
 Cholesterol also contributes to the formation of deposits on the inner walls of blood
vessels. These deposits harden and obstruct the flow of blood. This condition, known as
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atherosclerosis, results in various heart diseases, strokes, and high blood pressure
Lipids
 Adrenocorticoid Hormones: are products of the adrenal glands (“adrenal” means adjacent
to the renal (kidney).
 The most important mineralocrticoid is aldosterone, which regulates the reabsorption of
sodium and chloride ions in the kidney tubules and increases the loss of potassium ions
 Aldosterone is secreted when blood sodium ion levels are too low to cause the kidney to
retain sodium ions.
 If sodium levels are elevated, aldosterone is not secreted, so that some sodium will be lost
in the urine
 Aldosterone also controls swelling in the tissues

 Cortisol, the most important glucocortinoid, has the function of increasing glucose and
glycogen concentrations in the body
 These reactions are completed in the liver by taking fatty acids from lipid storage cells and
amino acids from body proteins to make glucose and glycogen
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Lipids
 In addition, cortisol and its ketone derivative, cortisone, have the ability to inflammatory
effects
 Cortisone or similar synthetic derivatives such as prednisolone are used to treat
inflammatory diseases, rheumatoid arthritis, and bronchial asthma.
 There are many side effects with the use of cortisone drugs, so there use must be monitored
carefully

 Waxes are esters of long-chain saturated and unsaturated fatty acids (having 14-36 carbon
atoms) with long-chain alcohol (having 16-30 carbon atoms)
 Waxes are typically water resistant and hard at room temperature, but they soften when
heated and liquefy if warmed adequately.
 Examples of animal waxes include beeswax and lanolin
 Plants also have waxes, such as the coating on their leaves, that helps prevent them from
drying out 21
Lipids L3: Lipids (contd.)
 Fruits produce a waxy coating to keep from drying out
 The cells in a Tulip make a wax which helps coat the leaves

 Ear wax traps dust, sand, and other foreign particles from going deeper into the ear and
causing damage

 Beeswax- a structural material to hold honey in the hive

 Beeswax is largely myricyl palmitate , the ester of myricyl alcohol and palmitic acid

 Carnauba wax, a major ingredients of car wax and floor polish, comes from the leaves of a
South American palm tree

 Waxes also coat skin, hairs and feathers, and help keep them pliable and water-proof.

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Lipids

WAXES

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 Nucleic Acids
 Nucleic acids include various DNA and RNA molecules
 They serve informational purposes
 DNA stores the genetic code, and various types of RNA help in the process
of interpreting that code to build proteins
 Certain RNAs can also function as catalysts
 Nucleic acids are the most important macromolecules for the continuity of
life
 They carry the genetic blueprint of a cell and carry instructions for the
functioning of the cell
Nucleic Acids
DNA and RNA
 The two main types of nucleic acids
 DNA is the genetic material found in all living organisms, ranging from
single-celled bacteria to multicellular mammals
 It is found in the nucleus of eukaryotes and in the organelles, chloroplasts,
and mitochondria
 In prokaryotes, the DNA is not enclosed in a membranous envelope
 DNA forms a complex with histone proteins to form chromatin, the
substance of eukaryotic chromosomes
 A chromosome may contain tens of thousands of genes
 Many genes contain the information to make protein products; other genes
code for RNA products
Nucleic Acids

DNA and RNA

 DNA controls all of the cellular activities by turning the genes on or off
 RNA, is mostly involved in protein synthesis.
 The DNA molecules never leave the nucleus, but instead use an
intermediary to communicate with the rest of the cell
 This intermediary is the messenger RNA (mRNA).
 Other types of RNA – like rRNA, tRNA, and microRNA – are involved in
protein synthesis and its regulation.
Nucleic Acids
 DNA and RNA are made up of monomers known as nucleotides
 The nucleotides combine with each other to form a polynucleotide, DNA or
RNA
 Each nucleotide is made up of three components: a nitrogenous base, a
pentose (5-carbon) sugar, and a phosphate group
 Each nitrogenous base in a nucleotide attached to a sugar molecule, which is
attached to one or more phosphate groups
 DNA has a double-helix structure
 The sugar and phosphate lie on the outside of the helix, forming the backbone
of the DNA
 The nitrogenous bases are stacked in the interior, like the steps of a staircase,
in pairs;
 the pairs are bound to each other by hydrogen bonds
 Every base pair in the double helix is separated from the next base pair by
0.34
Nucleic Acids
 The two strands of the helix run in opposite directions, meaning that the 5′
carbon end of one strand will face the 3′ carbon end of its matching strand
 This is referred to as antiparallel orientation and is important to DNA
replication and in many nucleic acid interactions
Macromolecules Natural polymers: organic and inorganic
 Some polymers are sometime classified as macromolecules: they include
cellulose, lignin, and various resins.
 Cellulose is a polysaccharide, a polymer that is composed of sugar molecules.
 Lignin consists of a complicated three-dimensional network of polymers
 Wood resins are polymers of a simple hydrocarbon, isoprene
 Another familiar isoprene polymer is rubber
 Rubber can be found in nature and harvested as a latex (milky liquid) from
several types of trees
 Natural rubber coming from tree latex is essentially a polymer made from
isoprene units with a small percentage of impurities
 Natural rubber does not handle easily (it's sticky), nor does it have very good
properties or durability
 Rubber can also be made synthesized
Macromolecules Natural polymers: organic and inorganic
 Synthetic rubber can be made from the polymerization of a variety of
monomers, including isoprene
 Vulcanized rubber is a synthetic (man-made) polymer
 Vulcanization changes the surface of natural rubber from very sticky to a
smooth, soft surface which does not adhere to metal or plastic substrates.
Macromolecules
• Pectin is a long chain polymer composed of pectic acid and pectinic acid
molecules
• Because these acids are sugars, pectin is called a polysaccharide
• It is obtained from citrus peels and the remains of apples
• In the plant/fruit, pectin is the material that joins the plant cells together
• Pectin chains form a network because some of the segments of the pectin
chains join together by crystallization
• Forming a three-dimensional network in which water, sugar and other
materials are held
• Formation of a gel is caused by physical or chemical changes that tend to
decrease the solubility of the pectin
• this favors the formation of small localized crystals
• The most important factor which influences pectin's tendency to gel is
temperature
Macromolecules
• The most important factor which influences pectin's tendency to gel is
temperature

• When cooling a hot solution containing pectin, the movement of the

molecules is decreased and their tendency to combine into a gel network is
increased
• This ability makes pectin a good thickener for many food products, like
jellies and jams.
• If there is sufficient sugar in the mixture, pectin forms a firm gel
What are macromolecule?

polynucleotide chain of deoxyribonucleic acid (DNA)