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Chapter V: LIPIDS
Chapter V: LIPIDS
Chapter V: LIPIDS
→ With three long-chain fatty acids, the triacylglycerol (fats) are ideal reservoirs for energy storage in the cell.
Phospholipids- forms lipid bilayers in water with their flexible tails in hydrophobic interior of the membrane and their polar
heads on the interior surfaces in contact with water.
→ Found in egg yolks, human nervous system and are in important component in plant, animal and microbial
membranes.
→ Organic compounds sharing a common physical property- solubility in non-polar solvents such as diethyl ether,
hexane, benzene, chloroform or carbon tetrachloride
→ Heterogeneous group of compounds including fats, oils, steroids, waxes and related compounds which are related
more by their physical rather than chemical properties
BIOMEDICAL IMPORTANCE
◼ Energy source- when oxidized, each gram of fat releases 9 kcal of energy.
◼ Cell membrane structural components- phosphoglycerides, sphingolipids and steroids make up the basic structure of
all cell membranes.
◼ Hormones- steroid hormones are critical chemical messengers that allow tissues of the body to communicate with one
another.
◼ Protection- fat serves as a shock absorber or protective layer for vital organs
◼ Insulation- fat is stored in adipose tissue where it also serves as a thermal insulator. Non polar lipids act as electrical
insulators allowing rapid propagation of depolarization waves along myelinated nerve
CLASSIFICATION OF LIPIDS
SAPONIFIABLE LIPIDS
Triglycerol Wax
s Phospholipids Sphingolipids
Monohydric; long chain Trihydric alcohol; alcohol
Fatty acid+ alcohol + phosporic
acid residue. Frequently have
Oils Fats nitrogen and others subs.
Sat<Unsat. Sat>Unsat.
Liquid Solid
Phosphoglyceride Plasmogens Sphingomlyins Glycolipids
Fatty acid+
sphingosine+
Carbohydrate
Steroids Terpenes
Prostaglandins & Leukotriene
FATTY ACIDS
◌ Are carboxylic acids used as building blocks for saponifiable lipids.
◌ Only a small amount of fatty acids are found in uncombined form in nature.
◌ Has a carboxyl group at the polar ends and a hydrocarbon chain at the non-polar tail.
◌ Are amphiphatic compounds because the carboxyl group is hydrophilic and hydrocarbon tail is hydrophobic.
-the more double bonds present, the lower the melting point. A
consequence of its presence in the cis geometry not in trans.
-the more double bonds/ DHA/ omega (nearesy methyl end of the
carbon chain) the better.
➢ Trans- like that of a saturated fatty acid in its fully extended formation; bad for health; low boiling point for
frying.
-a triacyglycerol containing three saturated acids of 12 carbons or more is solid at body temperature, where
as if the fatty aicds residues are 18:2, it is liquid to below 0 degrees celcius.
◌ Linoleic and linolenic acids are essential fatty acids they cannot be synthesized in the human body.
◌ All other fatty acids are non-essential fatty acids since they can be synthesized either from other fatty acids or from
carbohydrates and protein
GLYCERIDES- are lipid esters that contain the glycerol molecule and fatty acids
-these long molecules stack with one another and constitute the majority of the lipids
stored in the body’s fat cells.
► Phospoglycerides- have a polar region and phosphoryl group in addition to non-polar fatty acid tails
Esterification (alcohol+acid -> ester and water) - of glycerol with a fatty acid produces a neutral glycerides producing
monoglycerides, diglycerides, triglycerides.
◌ Animal fats- are mixtures of triacylglycerols or triglycerides (non polar, hydrophobic molecules, insoluble in water).
Are triesters of glycerol (1,2,3- propanetriol). Each of the three OH groups of glycerols forms an ester group by
reaction with the COOH group of a fatty acid to form the triacyglycerol.
- butter, beef, pork, poultry fats and vegetable oils such as corn, peanut, safflower, and olive oils
Coconut oil- liquid and derived from plants, so is still considered as oil
NOMENCLATURE
Ex. Tristearoylglycerol
→ other systematic way is naming first the glycerol portion as glyceryl then change -ic to o and the order is naming
first R1 then R2. The last two letters of R3 which is -ic is changed to -ate.
→ common name is based on the three fatty acids derived portion present in the structure.
→ the last two letter of the fatty acid derived portion, -ic is changed to -o. The first and second fatty acid derived
portion is separated to the second and to the third (R2 and R3) by a hyphen. The last two letter -ic of the name R3
is changed to -in.
→ Ex. Palmito-oleo-stearin
CHEMICAL REACTIONS
→ Are those expected of molecules containing ester and C=C functional group.
→ Hydrolysis of a triacyglycerol is the reverse of triacyglycerol formation (esterification) that yields glycerol and fatty
acids
→ Biological hydrolysis of a triacyglycerol occirs during digestion and requires the appropriate enzymes, referred to
as lipases
D. Rancidity
→ Fat and oil become rancid on standing (they develop disagreeble odors and tastes) through the processes
hydrolysis and oxidation.
→ Hydrolysis is important as a source of rancid odors only for certain triacyglycerols that contain C4 & C6 carboxylic
acids.
→ Butter is an example- its triacylglyerols contain 3-4% butanoic acid and 1-2% Caproic/ hexanoic acid. Hydrolysis
due to bacteria from the air releases these volatile and malodorous acids.
→ Air oxidation of the double bonds of unsaturated fatty acids released by bacterial hydrolysis also contribute to
rancidity.
→ Oxidation cleaves the double bond, with each carbon of the double bond being converted to a COOH group
WAX
→ Soluble in H20; Waxes from natural coatings on fruits, leaves, furs, feathers and skin
Ex. Lanolin (wool of sheep; (C48H69NO6), Beeswax, Carnauba wax, Spermaceti wax
PHOSPHOLIPIDS (PHOSPOACYLGLYCEROLS)
→ Polar head (phosphoryl group) and a non polar tail (alkyl chain of the fatty acid).
→ The most abundant membrane lipids are derived from glycerol-3-phosphate and are known as phosphoglycerides.
They contain acyl groups derived from long-chain fatty acids at C1 and C2 of glycerol-3-phosphate. At C3 the
phosphory groups I joined to glycerol by a phosphoester bond.
→ The simplest phosphoglyceride contains a free phosphoryl group and is known as phosphatidate.
→ Lecithin is an amphiphatic molecule. Its structure is similar to that of soap and detergent It is the major
phospholipid in pulmonary surfactant, alo found in egg yolks and soybeans. It is also used as an emulsifying agent
( aids in suspension of triglycerides in water) in ice cream. Emulsification occurs because the hydrophilic head of
lecitihin dissolves in
water and its hydrophobic
tail dissolves in
triglycerides.
SPHINGOLIPIDS
→ Composed of 1 molecule of the long chain amino alcohol sphingosine (or 4-sphingosine) or one of its derivatives,
1 molecule of a long-chain fatty acid, and a polar head group that is joined by a glycosidic linkage.
- oligosaccharides (polar head) + 1 or more residues of N-acetylneuraminic acid + Sialic acid (termini)
GLYCOLIPIDS
Carbohydrate bounds to an alcohol group of a lipid by glycosidic linkage, the resulting compound is a glycolipid.
Ceramides are usually the parent compound and the glycosidic bond is formed between the primary alcohol group of
the ceramide and a sugar residue. The resulting compound is called cerebroside (found in nerve and brain cells)
NONSAPONIFIABLE LIPIDS
→ Are not cleaved into a smaller molecules by hydrolysis because of the absence of esters.
→ Tetracyclic skeleton, consisting og three fused six-membered and one five- numbered ring.
→ The four rings are designated A, B, C, D as noted and peculiar numbering of the ring C atoms (shown in red) is the
result of an earlier misassignment of the structure. The substituents R are oftern alkyl groups, but may also have
functionality. The R group at the A:B ring fusion is most commonly methyl or hydrogen, that at C:D fusion is usually
methyl. The substituent C17 varies considerably and is larger that methyl if it is not a functional group.
-Cholesterol separates from the blood and deposits on the inner walls of arteries to form plaque. This narrowing of
arteries results in the heart working harder to pump blood, blood pressure increasing, and the heart enlarging over
time.
Medical practitioners generally make the following dietary recommendations to decrease the incidence of
cardiovascular disease:
-The major function of the cholesterol in the blood is synthesized in the liver. The body needs cholesterol and
manufactures all the cholesterol needed by various organ systems,
-Two types of lipoproteins carry most of the cholesterol in the blood stream, and they behave very differently from
each other as they move through the body:
➢ High-density lipoproteins (HDL) “good cholesterol”- HDLs move easily through the blood and are actually
beneficial to the body. They are stable and do not stick to artery walls. They help to prevent heart disease by
carrying cholesterol away from the arteries and back to the liver, where the process of their removal from the body
begins.
➢ Low-density lipoprotein (LDL) “bad cholesterol” - LDLs contain more fat and less protein than HDLs. They are
unstable and tend to fall apart. Rather than being removed from the body by the liver, they tend to stick to cells
lining the inside of artery walls.
➢ Chylomicrons (very low density lipoproteins VLDLs) and intermediate-density lipoproteins (IDLs)- Smallers
amounts of cholesterol may travel in “very bad” cholesterol
Higher surface area= faster hydrolysis---> fatty acid and cholesterol forms triglyceride--> Lipoprotein--> HDL or LDL
Different molecular forms of bile acids can be synthesized in the liver by different species. Bile acids are conjugated with taurine or
glycine in the liver, and the sodium and potassium salts of these conjugated bile acids are called bile salts.Bile salts are made of bile
acids that are conjugated with glycine or taurine. They are produced in the liver, directly from cholesterol. Bile salts are important in
solubilizing dietary fats in the watery environment of the small intestine. Once produced, but before being secreted into the
gallbladder or digestive system, bile salts are often bonded to glycine or taurine. Glycine is an amino acid, while taurine is derived
from the common amino acid cystine. This bonding increases the water solubility of bile salts. Glyco-bile and tauro-bile acids are also
referred to as conjugated bile acid.
Chromosomes- located in the nuclei of cells, contains genes, the fundamental unit of heredity. Two types of nucleic
acid are involved in carrying out the hereditary process:
1. Ribonucleic acid (RNA)- RNA molecules diffuse out of the ccell nucleus and carry out the critical tals of protein
synthesis in ribosomes, located in the cytosol.
2. Deoxyribonucleic acid (DNA)- contains hereditary information and directs reproduction of itself and the synthesis
of RNA.
Nucleotides- the building blocks (monomers) of nucleic acid. Are composed of simpler units: a base, monosaccharide,
and a phosphate.
BASES
Nucleoside: Sugar + Base. The purine bases are linked to C-1 of the monosaccharide through N-9 (the nitrogen at
position 9 of the five-membered ring) by β-N-glycosidic bond.
The pyrimidine bases are linked to C-1 of the monosaccharide though their N-1 by the β-N-glycosidic bond.
PHOSPHATE
-The third component of nucleic acid is phosphoric acid. When this group
forms a phosphate ester bond with the -CH2OH group of a nucleoside, the
result is a compound known as a nucleotide.
A. Primary Structure
1. A polynucleotide chain has a sense of directionality. The phosphodiester linkage between monomer units is between
the 3’ carbon of the monomer and the 5’ carbon of the next. Tus the two ends of a linear polynucleotide chain are
distinguishable. One end normally carries a uncreated 5’ phosphate, the other end an uncreated 3’ hydroxyl group
2. A polynucleotide chain has individuality, determined by the sequence of its bases- that is, the nucleotide sequence.
This sequence is called the primary structure of that particular nucleic acid.
B. Secondary Structure
1) Chargaff rule- that A&T and G&C are present in equimolar quantities
Concluded that DNA is composed of 2 strands intertwined around each other in a double helix
➢ 2 polynucleotide chains run in opposite directions (5’ -OH and 3’ -OH terminal)
➢ Sugar phosphate backbone is on the outside exposed to the aqueous environment, and the bases point inward.
The bases are hydrophobic. Through their hydrophobic interactions. They stabilize the double helix.
➢ The bases are paired according to Chargaff’s rule: A--T, C---G
DNA molecules are coiled atound basic protein molecules called histones. The acidic DNA and the basic histones attract
each other by electrostatic (ionic) forces, combining to form units called nucleosomes. In a nucleosomes, 8 histones
molecules from a core, around which 147-base-pair DNA helixin is wound. Nucleosomes are further condensed into
chromatin when a 30-nm-wide fiber forms in which nucleosomes are wound in a solenoid fashion, whith 6 nucleosomes
forming a repeating unit. Chromatin fibers are organized still further into loops, and loops are arranged into bands to
provide the superstructure of chromosomes.
RNA
1. Messenger RNA (mRNA)- carry genetic information from the DNA in the nucleus directly to the cytoplasm, where
the protein is synthesized.
- mRNA consists of a chain of nucleotides whose sequence is exactly complementary to that of one of the strands of
the DNA. This type of RNA is not long lived.
2. Transfer RNA (tRNA)- translates the genetic code of the mRNA into the primary sequence of amino acids in the
protein.
- have a cloverleaf-shaped secondary structure resulting from base pair hydrogen bonding A-U & G-C and roughly
shaped tertiary structure
- 3 nucleotides at the base of the coverleaf structure form the anti codon. This binds to a codon on a mRNA molecule
on the surface of a ribosome during protein synthesis.
3. Ribosomal RNA (rRNA)- ribosomes, which are small spherical bodies, locate in the cells but outside the nuclei,
contains rRNA.
4. Ribozymes (catalytic RNA)- spherical enzyme functions. Splicing in mRNA is catalyzed by ribozymes, which are
segments of mRNAs themselves.
- The central dogma of molecular genetics describe how hereditary information is transmitted and used to synthesize
proteins. Three fundamental processes take place in the transfer of genetic information:
Replication- is the pricess by which identical copies of DNA made so that information can be preserved and laded down
to offspring.
Transcription- is the process by which the genetic messages contained in DNA are read and carried out of the nucleus
to parts of the cell called ribosomes where protein synthesis occurs.
Translation- is the process by which the genetic messages are decoded and used to build proteins.
◌ REPLICATION
unwind from each other, and each acts as a template for synthesis of a
new, complementary strand. This results in two DNA molecules with one
one molecule that consists of both original DNA strands (identical to the
original DNA molecule) and another molecule that consists of two new
and daughter DNA. In this model, each individual strand is a patchwork of original and new DNA. (old &new, new
& old)
- The two strands of DNA double helix unwind over a short span to form a Replication bubble with a replication fork
at each end, two strands of DNA double helix unwind over a short span to form a replication bubble with a
replication fork at each end. Each strand act as template for synthesizing a complementary strand.
- Helicase and Topoisomerase enzymes catalyze the unwinding process: single-strand DNA-binding proteins
stabilize the unwound DNA, and DNA polymerase catalyzes the addition of nucleotide to growing DNA chains.
- The two new strands grow in opposite directions since each grows in the 5’ 3’ direction. The replication bubble
expands further unwinding the DNA template double helix as DNA synthesis occurs.
- These two forms a series of smaller DNA fragments referred to as Okazaki fragments, which are linked together by
- DNA polymerase directs the synthesis process by simultaneous complexation with the template DNA chain,
growing new DNA chain and nucleotide. Base pairing together with DNa polymerase control guarantees the
◌ TRANSCRIPTION
- In comparison of the sizes heaviest to lightest: DNA, rRNA, mRNA & tRNA
- The initially formed RNA, often referred to as primary transcript RNa (ptRNA), is altered by chemical reactions to
achieve biological activity.
- Post transcriptional processing of ptRNAs includes capping the ends of an RNA molecule with certain nucleotide
sequences, modification of certain nucleotide in the RNA chain, and splicing operations- involved cutting out
portions (introns) of rNA which do not appear to have any biological function. The portions (exons) with biological
function are linked together after excision of the introns.
- The cepping and splicing occur in the nucleus while most nucleotide modifications generally takes place in the
cytosol
◌ TRANSLATION
- Process by which rRNA, mRNA & tRNA come together to synthesize polypeptides.
RIBOSOMES- are formed from rRNA & also contain about 40% protein, mostly the various enzymes required for
protein synthesis. A ribosome is composed of two sub units, one large & one small.
- mRNa carrying the message for which polypeptide is to be synthesized, binds to the ribosome. Synthesis proceeds
when tRNAs transport various amino acids into the ribosome.
- The sequence of bases on the mRNA specifies the polypeptide to be synthesized. 3 consecutive bases (base
triplet)= codon (which specifies or codes for particular tRNA which carries a particular amino acid). Each tRNA has
a particular base triplet called anticodon.
The genetic code, the complete transcription of the amino acids specifies by various base triplets above. Note that the
codon sequence is always written in the 5’->3’ direction. The genetic code is universal it applies to all organism, plant
and animal.
► MUTATIONS
- Is a change in the sequence of bases in DNA. Spontaneous mutations result from errors in base pairing during
replication. Replication errors are very rare, less than 1 base pair per 10^10, because of the proof reading function
of DNA polymerase as well as the presence of various enzymes which have repair functions.
- Mutagens- agents that produce mutation. Includes UV (sunlight) & various high-energy radiations (x-ray, cosmic
rays, radioactivity) and variety of chemicals. Ex. Sodium nitrite
- Occurs by substitution, insertion, or deletion of bases. The insertion or deletion of a base causes frame shift- a
large change in the polypeptide sequence synthesized.
- Mutation that have negative biological consequences fall into two categories:
➢ In somatic cells (cells other that egg & sperm cells) affect the biological functioning of an organism.
Uncontrolled growth of cells (cancer) may result from mutation. A mutagen giving rise to cancer is referred to as
carcinogen.
➢ In germ cells ( egg & sperm cells)- have far-reaching significance since they are passed into offspring and
subsequent generations. Such mutations are referred to as genetic defects or hereditary diseases when biological
functions are severely affected
Ex. Albinism- absence of melanin; Cystic fibrosis- inadequate lipase produced by pancreas; Diabetes mellitus-
defective insulin; Galactosemia- defecting transferase, Hemophilia- defective blood clotting factors,
Phenyketonuria- lack of Phe hydroxylase for converting Phe to Tyr; Sickle cell anemia- defective hemoglobin;
Tay-Sachs- defective hexosaminidase
► ANTIBIOTICS
Most antibiotics fight bacterial infections by interfering with some aspect of protein synthesis in the bacteria.
Large-scale use of antibiotics has been highly successful but some bacteria have “fought back” by spontaneous
mutation and propagation of antibiotic-resistant strains. This requires that we keep ahead of the bacteria by
synthesizing new antibiotics to kill mutant strains.
Actinomycin Binds to DNA & prevents it from acting as template for both DNA & RNA synthesis
Erythromycin Binds to large sub unit of ribosome & prevents its movements along mRNA
Puromycin Binds to A site, become attached to growing peptide, & causes premature termination
Streptomycin Inhibits initiation & causes incorrect reading of mRNA by bing to rRNA
► VIRUSES
- Are infectious, parasitic small particles containing either DNA or RNA (but not both) encapsulated by a protein
overcoat.
- At the border line of life since they neither reproduce nor carry out metabolism because they lack most of the
apparatus (amino acids, nucleotides & enzymes) for replication, transcription & translation. Virus uses the
apparatus of the host cell to reproduce itself. Retrovirus are RNA viruses that reproduce through the intermediate
formation of DNA. The retrovirus contains the genetic information for the synthesis of the enzyme reverse
transcriptase.
Also referred to as genetic engineering or cloning involves the alteration of the DNA of some organism with the
objective of having that organism produce a desired polypeptide. The E. coli bacterium is most often used, although
yeast have also been employed.
CHAPTER VII: DIGESTION
-Foods are enzymatically degraded to low-molecular weight components to prepare them for absorption in the gut.
1. Mouth- with mechanical action of chewing and the secretion of carbohydrase, amylase in the saliva
2. Stomach- where secretion of the hormone gastrin is stimulated by the entry of protein into the stomach. Gastrin in
turn, stimulates the secretion of:
◼ Pepsinogen- by the chief cells of the gastric glands. Is called a zymogen or inactive enzyme precursor which is
activated by the enzymatic action of trace amounts of pepsin already present in the stomach.
- Pepsin attacks the peptide bonds of amino acids possessing hydrophobic side groups, which
reduces proteins to mixtures of smaller peptides.
- Other enzymatic hydrolases which are found in the small intestine are also secreted as zymogens,
and are activated by similar processing.