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Scope of Biochemistry: Functional Group
Scope of Biochemistry: Functional Group
Acids: carboxyl RCOOH Weakly acidic; proton Fats & amino acids
donor
Classification of Carbohydrates
Amylopectin - glycogen-like
structure, ⍺ 1,6 linkages at 1
in 30 monomers
Non - starch Cellulose - insoluble
- Main
constituent of
plant cells and
vegetable fiber
e.g. cotton
- Chains of
glucose
monomers
Hemicellulose -
polysaccharides of simpler
structure than cellulose
- Any of a class
of substances
which occur as
constituents of
plant cell wall
Isomers - molecule with the same formula as another molecule but different chemical properties
- Same number of atoms of each element, different arrangement
2 types:
● Constitutional (structural)
● Stereoisomer (spatial) - same structural formula, different spatial configuration
○ Carbohydrates - 1 or more chiral centers (carbon with 4 different groups
attached) = possibility of stereoisomers
○ Number of asymmetric or chiral carbon atoms (n) = possible isomers of a given
compound (2n)
○ Ex. glucose with 4 chiral carbon atoms has (24) 16 possible isomers
○ 2 types:
■ Enantiomers - non-superimposable mirror images of each other
- Optical isomers
- Similar physical properties
- Positive (+) - dextrorotatory
(right)(clockwise)
- Negative (-) - levorotatory
(left)(counterclockwise)
Step 3:
● Sets to form a bond between the C-5 -OH and the carbonyl carbon (C-1) to make a new
ring
● Make the stereochemistry of the ring clearer
● Interchanging any three groups on a carbon does a bond rotation
● Three “moves”: H→OH
■ OH→CH2OH
■ CH2OH→H
Step 4:
● Draw the C5 -OH attaching the carbonyl carbon, forming a new O-C1 single bond and
breaking the C1-O pi bond
● After proton transfer, we now have one of two rings (haworth projections)
● All the groups that were pointing “up” in the linear model (ex. C3 -OH) also point “up” in
the haworth
● All the groups that point “down” in the linear model (ex. C2 -OH and C4 -OH) point
“down” in the haworth
● One exception: C1 oxygen, can be “up” (β) or “down” (α) according to which face of the
carbonyl is attacked
Haworth projections for five-membered ring sugar (i.e. furanose)
● The shortcut is essentially the same, but since the C4 -OH is usually forming the ring
instead of C5 -OH, the mnemonic right → down, left → up only apply to two carbons
adjacent to the carbonyl (usually C2 and C3)
● If the C4 -OH is forming the ring, and if it’s on the right in the fischer (i.e. D, for a
pentose), then the C5 will point up on the haworth
● α and β are assigned by comparing the orientation of the C1 -OH with the C4 substituent
(not the C5 substituent as with a pyranose)
● C4 -OH points to the right in the fischer and the C5 substituent (CH2OH) points up in
haworth
Mutarotation - a difference in the specific rotation of plane-polarized light, due to the change in
the equilibrium between two anomers in the solution
- Configuration is specified as a prefix to the IUPAC name (CIS, TRANS, SYN,
ANTI, E, Z, R, S, etc.)
- Molecule must have hemiketal (an alcohol and ether attached to the same
carbon, along with two other carbons) or hemiacetal group
- First observed in sugar
- Specific rotation of sugar in aqueous solution varies from sugar to sugar
Chemical Reactions of simple sugars
Monosaccharide general formula: Cn(H2O)n
Functional groups:
Aldehyde Ketone
Reactions:
● Oxidation - aldehyde group or ketone group or terminal hydroxyl group oxidized to form
acids
-
● Reduction - aldehyde or ketone group forms alcohol
- Glucose - Sorbitol
- Galactose - Dulcitol
- Mannose - Mannitol
- Fructose - Mannitol + Sorbitol
● Phenyl Hydrazine - in acidic condition, forms osazone
- Structures of osazone
- Glucose and Fructose - Needle shaped
- Lactose and Galactose - Fluffy ball shaped
- Maltose - Sunflower shaped
● Esterification - gives Glucose-1 phosphate or Glucose 6 Phosphate
● Dehydration - when treated with concentrated sulfuric acid, releases 3H2O = furfural
- Furfural - chemically active
- Can react with phenolic compound
- + α Napthol (phenolic compound) = colored product
● Tautomerization - shifting of hydrogens from one carbon to the other to form any diols
Note: many polysaccharides become covalently bonded with lipids and proteins to form
glycolipids and glycoproteins that send messages between and within the cells
Lipids - form a group of organic compounds which are widely distributed in living organisms.
- Made up of carbon, hydrogen and oxygen but the proportion of oxygen is much less than
2:1.
- Most lipids are esters formed by condensation of alcohols and fatty acids.
- Insoluble in water
- Soluble in organic solvents (e.g. chloroform, alcohol, acetone, etc.)
Functions
● Precursors of hormone
● Helps in digestion
● Energy storage
● Metabolic fuel
● Part of cell membrane
● Protection and lubrication
Simple Lipids - consist of long chain fatty acids which may be either free or combined with an
alcohol by an ester linkage
- Main simple lipids are triglycerides (aka triglycerols), steryl esters and wax
esters
- Hydrolysis of these lipids yields glycerol and fatty acids (for triglycerides), sterol
and fatty acid (for steryl esters), fatty alcohols and fatty acids (for wax esters)
Triglycerides - most important
- Major components of edible oils and fats, often representing more than
95% of refined oils
- Esters of the trihydric alcohol glycerol with 3 fatty acids
Structure of triglycerides
- Glycerol - hydrophilic : attracts water
- Fatty Acids - are carboxylic acids with hydrocarbon side chains.
- the simplest form of lipids and they are water soluble.
- exist in the body either as free acids or fatty acyl esters such as
triacylglycerol.
- are released from these lipids on hydrolysis by lipases.
- Divided into: saturated and unsaturated
Structure of Triglycerides
Green - glycerol
Red - fatty acids
Simple (pure) glyceride - 3 hydroxyl groups are esterified with same type of fatty acid
- Ex. Tristearin
Mixed glyceride - 3 hydroxyl groups are esterified with different type of fatty acid
Wax - are esters of long-chain (C14 to C36) saturated and unsaturated fatty acids with
long-chain (C16 to C30) alcohols.
- Melting points (60° to 100°C) generally higher than those of triglycerides
- Unusually inert due to saturated nature of the hydrocarbon chain
- Can be split slowly with hot alcoholic KOH
- Insoluble in water
- Highly resistant to atmospheric oxidation
- Most waxes are mixtures of esters
- Chief storage form of metabolic fuel for planktons
- Certain skin glands of vertebrates secrete waxes to protect hair and skin and keep it
pliable, lubricated, and waterproof
- Shiny leaves of holly, rhododendrons, poison ivy, and many tropical plants are coated
with a thick layer of waxes, which prevents excessive evaporation of water and protects
against parasites
- Examples of biological waxes:
- Plant waxes - coats leaves and stems
- Beeswax - abdominal glands of bees
- Lanolin - sheep’s wool
- Cerumen - ceruminous gland in ear
- Suberin - bark of trees
- Sebum - sebaceous gland
- Application of biological waxes:
- Pharmaceutical, cosmetic, and other industries
- Lanolin, beeswax, canauba wax (from a brazilian palm tree), and wax extracted
from spermaceti oil (from sperm whale) are widely used in the manufacture of
lotions, ointments, and polishes
- Triacontanoylpalmitate - major component of beeswax
- Ester of palmitic acid with the alcohol triacontanol
- Structure
Conjugated lipids - esters of fatty acids with alcohol but contains extra groups
Classifications:
● Phospholipids - phosphoglycerides
- Membrane lipids
- 2 fatty acids are attached in easter linkage to the first and second
carbons of glycerol
- A highly polar or charged group is attached through a
phosphodiester linkage to the third carbon
- Special property: amphipathic
- Has polar and nonpolar ends:
- Polar hydrophilic - phosphate group attached to glycerol
and a positively charged base
- Nonpolar hydrophobic - two long fatty acids
- Arranged as bilayer because of polar and nonpolar ends
Important phospholipids
● Lecithins - framework of cell, nuclear membrane, etc.
● Cephalins - play important role in blood clotting
● Sphingophospholipids - cell membranes, myelin sheath of axons
● Glycolipids - complex lipids with one or more simple sugars, with long chain
fatty acids or alcohols
- Ex. cerebrosides - white matter of brain cells and myelin sheath
of nerve
- Gangliosides - gray matter of brain
Derived Lipids - includes a large variety of highly lipid-like compounds derived from the
intermediates of lipid metabolism
- These compounds can be classified into 2 main groups or more units of a common
precursor molecule (isoprene)
- Isoprene - 5 carbon compound derived from condensation of Acetyl coenzyme A
molecule
- Terpenes - steroids, sterols, fat soluble vitamins, bile salts, pigments, etc.
- Steroids - not formed from fatty acids but have lipid-like characteristics
- Possess 17 carbon nucleus of 4 fused hydrocarbon rings
- Various steroids differ in the number and position of double bonds between
carbon atoms and in the side group linked to the ring.
- Ex. sterols like cholesterol (constituent of membranes; source of steroid
hormones), ergosterol, bile salts, sex hormones, pigments, cortisol (secreted by
adrenal gland), Vitamin D2 (produced in the skin by the action of light on a
cholesterol derivative)
- Icosanoid - has 3 types:
- Prostaglandins - hormone-like compounds
- Hydroxy derivatives of 20 carbon polyunsaturated
fatty acids
- Found in human seminal fluid, uterus, stomach,
lungs, etc.
- Functions:
- Inflammation
- Allergic reaction
- Blood clotting
- Smooth muscle contraction
Nucleic acid
Nucleotides - building blocks of nucleic acid
- Contain Carbon, Hydrogen, Oxygen, Nitrogen and Phosphorus
- Made up of 3 components:
- Ribose sugar - 5-carbon pentose sugar molecules
- Represented by either ribose sugar ( C5H10O5) or
deoxyribose sugar (C5H10O4)
- Phosphoric acid - made up of 3 acid groups
- Acid groups react with OH group of ribose or deoxyribose
to form pentose monophosphate esters
Higher nucleotides (energy carriers) - nucleotides with more than one phosphate molecule
● ADP - Adenosine diphosphate
● ATP - Adenosine triphosphate
● CDP - Cytidine diphosphate
● CTP - Cytidine triphosphate
● TDP - Thymidine diphosphate
● TTP - Thymidine triphosphate
● GDP - Guanosine diphosphate
● GTP - Guanosine triphosphate
● UDP - Uridine diphosphate
● UTP - Uridine triphosphate
High energy or energy rich bond - Linkage of additional phosphate groups involves large
amounts of energy.
- provided by the oxidation of food.
- Separation of phosphate groups release large amounts of energy
- Bonds joining the additional phosphate groups to nucleotides
History of DNA
● Phoebus Levene (1869-1940) - had discovered that the cell nucleus contains 2 types of
nucleic acids: DNA and RNA
- Found that DNA contained the four bases, deoxyribose,
and a phosphate group
● Erwin Chargaff - published a paper stating that in DNA of any given species, the ratio of
adenine to thymine is equal, as is the ratio of cytosine to guanine (1950).
- This is known as “Chargaff’s ratios” and was a crucial clue that
helped solve the structure of DNA
- Chargaff’s ratios are universal: all forms of life obey this rule
- Only the balance of A-T pairs and C-G pairs varies between
species
● Rosalind Franklin - together with Raymond Gosling obtained x-ray diffraction pattern,
which triggered the idea that DNA was a helix
- She produced the x-ray crystallography pictures of DNA which
Watson and Crick used to determine the structure of
double-stranded DNA
● Watson and Crick - James D. Watson and Francis Crick were the two co-discoverers of
the structure of DNA in 1953
- Used x-ray diffraction data collected by Rosalind Franklin and
proposed the double helix or spiral staircase structure of the DNA
molecule
● Two polynucleotide chains are coiled around a central axis in the form of a right handed
double helix.
● The backbone of each strand consists of alternating sugar and phosphate. The bases
project inwards and they are perpendicular to the central axis.
● The 2 strands run in opposite directions (ie.) they are antiparallel. Each polynucleotide
chain has 5’ phosphorylated and 3’ hydroxyl ends
● The strands are complementary to each other due to specific base pairing of the
opposite strands. Base pairing occurs through hydrogen bonding and it is specific.
Adenine pairs with thymine through two hydrogen bonds. Guanine pairs with cytosine
with three hydrogen bonds.
● Major and minor grooves are present on the double helix.
● One turn of helix measures 34 angstrom and has 10 nucleotides.
● Distance between adjacent nucleotides is 3.4 angstrom.
● The diameter of the helix is 20 angstrom.
FUNCTIONS OF DNA
● Carries hereditary information.
● Controls the metabolic activity of the cell.
● Enables cell to maintain, grow and divide.
● Contributes to variation by undergoing mutation.
● Brings about differentiation of cells
RIBONUCLEIC ACID (RNA) - are present in the nucleus, ribosomes and cytoplasm of
eukaryotic cells.
- Function as genetic material for some plant virus, animal viruses and bacteriophage.
- Are also polynucleotides. In RNA polymer, purine and pyrimidine nucleotides are linked
together through phosphodiester linkages. The sugar present is ribose. The nitrogenous
bases present in RNA are adenine and guanine (purine bases), uracil and cytosine
(pyrimidine bases).
3 Types of RNA
Messenger RNA (m RNA) - accounts for 1-5% of cellular RNA.
- Single stranded linear molecules consist of 1000-10,000
nucleotides
- Have a free or phosphorylated 3’ and 5’ end.
- A direct carrier of genetic information from the nucleus to the
cytoplasm.
- Contains information required for the synthesis of protein
molecules.
FUNCTIONS OF RNA
● Protein synthesis
● Genetic material
● Component of ribosomes
● Associated with DNA replication
● Some RNA have enzymatic activity (ribonuclease)
Difference between DNA and RNA