LEC NOTES – LIPIDS

Saturated Fatty Acids

 straight-‐chain, single-‐bonded carboxylic acids (C10-‐C20)
 have even number of carbon atoms because these FA are built from “acetic acid” units
 insoluble in H2O because of the long HC chain
 solids at room temperature (high melting points) because of the close, regular packing of the
HC chain
 in coconut oil (liquid at room temperature) because it is composed mainly of lauric acid (C12),
short-‐chain fatty acid
 found abundantly in animal FATS; resist oxidation

Unsaturated Fatty Acids

 may be mono-‐ or polyunsaturated (two or more, “cis” double bonds)
 liquids at room temperature (low melting points) because the cis double bonds interrupt the
regular packing of the HC chains
 essential fatty acids – linoleic (C18), linolenic (18) and arachidonic (C20); polyunsaturated, not
synthesize in the body therefore must be included in the diet
 found abundantly in vegetable OILS; can undergo oxidation producing short-‐chain aldehydes
and carboxylic acids
 can also undergo hydrogenation producing saturated FA

Omega-‐3 Fatty Acids

 polyunsaturated fatty acids found abundantly in marine animals: linolenic (C18),
eicosapentaenoic acid “EPA” (C20) and docosahexaenoic acid “DHA” (C22)
 associated with low occurrence of atherosclerosis and heart attacks even in a high-‐fat diet and
high levels of cholesterol (HDL)
 lower the ability of platelets to form “blood clots”
 omega-‐3: double bond at C3 farthest from the –COOH group
 omega-‐6, polyunsaturated fatty acids found abundantly in vegetable oils e.g. linoleic (C18) and
arachidonic acids (C20)
LINOLEIC ACID (C18)
COOH

EICOSAPENTAENOIC ACID (C20)

COOH
Prepared by: Asst. Prof. Marites D. Saludares, PhD / Chemistry Department, UST College of Science / [email protected]
 DOCOSAHEXAENOIC ACIDS (DHA)
COOH
Prostaglandins
 fatty acid and hormone-‐like substances, initially believed to originate in the prostrate gland
 synthesize in the body from arachidonic acid (C20)
 “eicosanoids”, Greek eikosi – twenty
Physiological Effects of Prostaglandins:
1) activation of the inflammatory response in the joints (rheumatoid arthritis)
2) production of fever
3) production of pain
4) induction of blood clotting
Synthesis of Prostaglandins
ARACHIDONIC ACID
COOH

PGH2 -‐ synthase
COOH
HO

HO

PROSTAGLANDIN

Inhibition of the Synthesis of

Prostaglandins: aspirin (ASA)
PGH2 – synthase
COOH + --‐ ‐-‐-‐-‐CH2O – H

O-C-CH3
O

COOH
+ PGH2 – synthase --‐ ‐-‐-‐-‐-‐CH2O – C – CH3 acetylated enzyme
II
OH O

Prepared by: Asst. Prof. Marites D. Saludares, PhD / Chemistry Department, UST College of Science / [email protected]
 Triglycerides
 also known as triacylglycerols; “stored fat” and source of energy
 a triglyceride is an ester formed between glycerol and 3 FA
 being an ester may undergo base hydrolysis or saponification producing glycerol and 3 long-‐
chain carboxylate salts (SOAP)
composition:
 glycerol (Acrolein test) Potassium bisulfite
 fatty acids (Br2 H2O – test for unsaturation)

Waxes
 high molecular weight, solid esters
 served as protective coating in plants to help prevent loss of water and damage from pests
 in animals to provide water – proof coating
composition:
 a long-‐chain alcohol (monohydric)
 1 FA

Phospholipids
 also known as glycerophospholipids
 contain both hydrophilic and hydrophobic regions that allow them to interact with polar and
non polar substances
 most abundant lipids in cell membranes because of their role in “cellular permeability”
 combined with protein (lipoproteins), transport insoluble lipids e.g. triglycerides and
cholesterol in the body
composition:
 glycerol backbone
 2 FA
 phosphoric acid
 nitrogen-‐containing compound (may be choline, ethanolamine, serine)
Phosphatidyl Choline
 also known as lecithin
composition:
 glycerol
 2 FA
 phosphoric acid
 choline (a quaternary amino alcohol)
CH3
l
HO-‐CH2CH2 -‐ N+ -‐ (CH3)3
l
CH3

Phosphatidyl Ethananolamine
 also known as cephalin
composition:
 glycerol
 2 FA
 phosphoric acid
 ethanolamine (an amino alcohol)
HO-‐CH2CH2 -‐ NH2
Phosphatidyl Serine
composition:
 glycerol
 2 FA
 phosphoric acid
 serine (an amino acid) containing an α-‐amino group;
(+) Ninhydrin test -‐ blue violet solution, presence of an α-‐NH2/ α-‐NH group
HO-‐CH2CH – NH2
l
COOH

Sphingolipids
Sphingomyelin
 a ceramide (amide linkage formed between the –NH2 of sphingosine and -‐COOH of FA )
 one of the most abundant sphingolipids; protective coating of the myelin sheath that ensures
speed of nerve impulses
composition:
 backbone: sphingosine (a high molecular weight amino alcohol)
 1 FA
 phosphoric acid
 choline
Glycolipid
 also known as cerebrosides [ceramide (sphigosine and FA) and sugar]
 gangliosides – has two or more sugar units
composition:
 backbone: sphingosine (a high molecular weight amino alcohol)
 1 FA
 galactose, (+) Molisch Test – violet ring, general test for carbohydrates

CH3(CH2)12CH=CH-CH-OH
CH-NH-C-(CH2)12CH3
CH OH

OH
2
O CH2 O
O
OH

OH
Cholesterol
 synthesize by the liver from fats, carbohydrates and proteins to form:
 part of cell membranes, brain and nerve tissues
 steroid hormones
 bile salts
 also found in skin as precursor of Vitamin D
CH3 CH3

CH3 CH3

CH3

OH
cyclopentanoperhydrophenanthrene ring
(sterol nucleus)
Bile Salts
 synthesized in the liver from cholesterol and stored in the gall bladder
 act as emulsifying agents
 gallstones: high levels of cholesterol in the gall bladder causing “precipitation”
 jaundice: gallstones obstructing the bile duct, bile cannot be secreted and bile pigments
(bilirubin) enter the blood
OH
CH3 C-N-CH -C O
2
OH O-Na+
CH3

CH3

OH OH
 Lipoproteins
 lipids must be transported through the bloodstream for:
 energy storage
 synthesis of cell membranes, nerves and tissues, hormones and bile salts
 lipoproteins: phospholipids and proteins as “carriers” of insoluble lipids
 LDL “bad cholesterol”: deposit excess cholesterol in the arteries (atherosclerosis) and risk of
myocardial infarction
 HDL “good cholesterol”: remove excess cholesterol from tissues, carry them back to the liver,
for elimination as bile salts
 high-‐fat diet (saturated FA) causes:
 reabsorption of cholesterol from bile salts
 liver to increase its synthesis of cholesterol

Lipoproteins Origin Compounds Targeted Function

Transporte Cells/
d Tissues
chylomicrons intestinal exogenous lipids adipose stored energy
mucosa
VLDL liver endogenous lipids adipose; stored energy
extrahepatic tissues
LDL liver cholesterol and other extrahepatic tissues; synthesis of cell membranes,
endogenous lipids arteries (x’ss hormones and bile salts
cholesterol)
HDL liver cholesterol (as products of liver elimination as bile salts
metabolism)
 Cell Membrane
 lipid bilayer (fluid mosaic model): two rows of phospholipids –
hydrophobic tails -‐ at the center
hydrophilic heads -‐ at the outer edges
composition:
 phospholipids (unsaturated FA) allow “fluidity”
 cholesterol provides strength and rigidity
 peripheral proteins
 integral proteins or “protein channels” for facilitated transport (e.g. glucose)
 sphingolipids and glycolipids for cell recognition and communication
HW – LIPIDS
For nos. 1-‐2, refer to the given lipid structure:
O
CH2-O-C-(CH2)16CH3

CH-O-C-(CH2)16CH3
O NH3+

CH2-O-P-O-CH2-CH-COO-
O
1) Identify the lipid structure, give its role/ function, and enumerate its hydrolysis products or
components.

Answer: It is a phosphatidylserine, known for its role in cellular permeability as it acts as the
barrier. It’s components are a glycerol backbone, 2 FA, phosphoric acid, and a nitrogen-‐
containing compound in this case serine.

2) Explain which hydrolyzed component will be positive in the Acrolein test? Ninhydrin test?

Answer: For the Acrolein test to have a positive result, the potassium bisulfite must react with the
glycerol to produce the acrolein. And for the Ninhydrin test it is the nitrogen containing
compound as Ninhydrin test detects amino groups.

For no. 3, refer to the given lipid structure:

O

CH2-O-C(CH2)7-CH=CH-(CH2)7-CH3
O

CH-O-C-(CH2)16CH3
O NH3+

CH2-O-P-O-CH2-CH-COO-
O
3) Explain which hydrolyzed component will be positive in the Br2 water test.
Answer: The phospholipid contains an unsaturated fatty acid called Oleic also known as cis-9-
Octadecenoic which will give the Br2 H2O test a positive result as it detects unsaturated fatty
acid.
For no. 4, refer to the given lipid structure:
CH3(CH2)12-CH=CH-CH-OH
O

CH-NH-C-(CH2)12CH3
O
CH2-O-P-O-CH2CH2-N+(CH3)3
O

4) Will the given lipid be positive in the Ninhydrin test? Explain.

Answer: Yes since the Phosphatidylehtanolamine has ethanolamine which has an amino
group.
For no. 5, refer to the given lipid structure:
CH3(CH2)12CH=CH-CH-OH

CH-NH-C-(CH2)12CH3
CH OH
OH 2 O O CH2 O
OH

OH
5) What test will identify this lipid?

Answer; This glycolipid can be identified by Molisch test as it has a Glucose and the test is for
generic carbohydrates.

6) Explain what kind of product is formed if NaOH is added to a triglyceride? Discuss the principle
how the product can help in the fight against the coronavirus.

Answer: When NaOH is added to a triglyceride considering glyceride is an ester, adding a base
to it like NaOH will produce alcohol and salt, for this case a carboxylic fatty salt, or soap. Soaps
have long uncharged hydrocarbon tails and a negatively charged terminus which actually
dissolves oil and emulsifies even viruses rendering it harmless.

7) Discuss why a saturated fatty acid like coconut oil has a good anti-‐oxidant property.

Answer: it was said the level of unsaturation is connected to the attraction of oxidation. Since
the oil is saturated then it will more than likely reject oxidation.

8) What are essential fatty acids? Cite some clinical signs of essential fatty acid deficiency.

Answer: Essential fatty acids are fatty acids that cannot be produced by the body hence must
be taken through diet and is necessary for some specific biochemical functions.
Alpha-lenolenic acid and linoleic acid are essential fatty acids. These ones are important as they
are mandatory in the making of arachidonic acid, the precursor of the 20-carbon fatty acids
called eicosanoids. Eicosanoids include three groups: (a) prostaglandin, (b) thromboxanes, (c)
and leukotrienes. All of these have different roles in the body. Example in blood clotting
Thromboxane A2 causes blood clotting to reduce further blood loss.

9) Why are the essential fatty acids associated with low incidence of heart disease?

Answer: essential acids like alpha linolenic acid and linoleic acids are used for the biosynthesis
of arachidonic, the precursor of eicosanoids. Prostacyclin a prostaglandin(eicosanoids), is an
antagonist to Thromboxane A2 as it reduces the chance of blood clotting which if not
maintained properly may cause a higher pressure in the blood vessels causing stroke and other
cardiovascular related diseases.
10) What are the physiological effects of prostaglandins? Explain how aspirin can block the
synthesis of prostaglandins?

Answer: Prostaglandin affects blood clotting, inflammatory response, reproduction,

gastrointestinal tract’s protection of lining, kidney’s electrolyte secretion, and
bronchodilation in the lungs. Aspirin is capable of blocking the enzyme,
cycloozygenase, COX-1, and COX-2, which are important for the conversion of
arachidonic acid into protaglandines. Prolonged blocking of prostaglandins might
cause damage in the GI-tract of the body.

11) In terms of structure, how is cholesterol different from bile salts? Cite causes of bile duct
obstruction and symptoms.

Answer: Both cholesterol and bile salt have the typical isoprene and steroid nucleus of
steroids. The difference is that there is carbonyl group in the bile salts’ conjugation site
while there isn’t one in cholesterol. Bile duct can be obstructed with the formation of
gallstones. Gallstones can be produced if too much cholesterol is in the gall bladder. If
the bile duct is obstructed then bile in the bile duct cannot be easily expelled that is why
the pigments of the from the bile increase in numbers and starts to enter the
bloodstream giving of an unhealthy yellow color to the patient, this is called jaundice.

12) Explain the cell membrane’s lipid bilayer. What are the lipids found in the cell membrane?

Answer: There are the phospholipids, sphingolipids, the glycolipids, and cholesterol.
The cell membrane is important in the transporting of nutrients. It is mainly composed of a lipid
bilayers with a hydrophilic head and hydrophobic tails eith “kinks” allowing them to not pack
tightly and are the “fluid” part of the bilayer. There are also sphingolipids glycoproteins for
detection, and communication. Cholesterol provides the strength of the cell membrane.
References:

1. Coconut Oil. (n.d.). Retrieved September 11, 2020, from

https://www.sciencedirect.com/topics/neuroscience/coconut-oil

2. Katherine Denniston and Joseph Topping and Danae Quirk Dorr. (2019, January 09).
General, Organic, and Biochemistry. Retrieved September 11, 2020, from
https://www.mheducation.com/highered/product/general-organic-biochemistry-
denniston-topping/M9781260148954.html

3. Libretexts. (2020, July 14). 19.6: Aspirin, Arachidonic Acid, and Prostaglandins. Retrieved
September 11, 2020, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map
%3A_Organic_Chemistry_%28Smith
%29/Chapter_19%3A_Carboxylic_Acids_and_the_Acidity_of_the_O
%E2%80%93H_Bond/19.6%3A_Aspirin%2C_Arachidonic_Acid%2C_and_Prostaglandins