BIOCHEMISTRY

LIPIDS
Dr. Rogelio Loluquisen | October 16, 2019
Trans by: Emily Joy Bacud

o Phospholipids - FA + alcohol (glycerol/ sphingosine-

OUTLINE amino) + Lipids, a phosphoric acid residue.
I. LIPIDS - They frequently have nitrogen-containing bases (eg,
II. LIPOGENESIS choline) and other substituents. sphingosine, which
III. FUNCTIONS OF LIPIDS contains an amino group.
IV. CLASSIFICATION OF LIPIDS
V. FATTY ACID
- main lipid constituents of membranes
A. Saturated FA - Derivatives of phosphatidic acid
B. Unsaturated FA - Phosphate is esterified with one –OH group of
V.TRIACYLGLYCEROL (TRIGLYCERIDES) glycerol and other two –OH are esterified to two long
VI. AMPHIPHATIC LIPIDS chain FA (glycerophospholipids)
VII. CLINICAL CORRELATIONS
- Intermediate in the synthesis of triacylglycerol and
VIII. IMPORTANT TO KNOW
IX. LIPID PEROXIDATION
phosphoglycerols
X. REFERENCES Phosphatidylcholines Most abundant phospholipid
(lecithins) in cell membraine
large proportion of body’s
I. LIPIDS
store of choline
▪ heterogeneous group of compounds, including fats, Phosphatidylinositol cleaved precursor of second
oils, steroids, waxes, and related compounds, more w/ diacylglycerol and messenger
physically related. They are: inositol tris-phosphate
- relatively insoluble in water (compartmentalized) Cardiolipin major lipids of mitochondrial
- (2) soluble in nonpolar solvents (ether, chloroform) membranes
Decreased cardiolipin levels
II. LIPOGENESIS or alterations cause
mitochondrial dysfunction
▪ Synthesis of FA, specially palmitate
in aging and including heart
▪ Location: liver, kidney, lung, mammary gland,
failure,
adipose, cytosol
hypothyroidism, and Barth
▪ Immediate substrate: Acetyl CoA
syndrome
▪ Product: Palmitoyl CoA
▪ RLS: Acetyl CoA + HCO3 + ATP → Malonyl CoA Lysophospholipids have implications in
▪ RLE: Acetyl CoA carboxylase promoting atherosclerosis
Plamogens occurs in brain and muscles
Destroys reactive oxygen
III. FUNCTIONS OF LIPIDS
species
a. important in diet Sphingolipids found in CNS
- high energy value of fats (Sphingomyelins) myelin sheath - makes
- essential fatty acids axons a very good nerve
- fat soluble vitamins (A,D,E,K) impulses conductor
b. thermal insulator (storage: adipose tissue) Phosphatidylethanolamine 1. also found in cell
c. beneficial in CVD, RA and dementia (long chain ɷ 3 (cephalin) membranes
fatty acids) phosphatidylserine 2. differ from
d. electrical insulators, allowing rapid propagation of
phosphatidylcholine only in
depolarization waves along myelinated nerves.
that ethanolamine or serine,
(nonpolar lipids)
respectively, replaces
choline
IV. CLASSIFICATION OF LIPIDS Dipalmitoyl lecithin 3. surface-active agent and a
1. Simple lipids - esters of fatty acids with various alcohols: major constituent of the
o Fats: Esters of fatty acids + glycerol surfactant preventing
o Oils are fats in the liquid state adherence, due to surface
o Waxes: Esters of fatty acids + higher MW tension, of the inner
monohydric alcohols surfaces of the lungs
2. Complex lipids - esters of fatty acids containing groups +
alcohol + one or more fatty acids.

Trans # 9 Bacud 1 of 4
 Phosphorylated 4. important part in cell # of C Common Occurrence
phosphatidylinositols signaling and membrane Name
(phosphoinositides) trafficking 2 Acetic Major end product of CHO
lysophosphatidylcholine 5. imp. in the metabolism and fermentation by rumen org.
(lysolecithin) interconversion of 4 Butyric -Butter
phospholipids. -End product of CHO
6. found in oxidized fermentation by rumen org.
lipoproteins promote 5 Valeric
atherosclerosis 6 Caproic
12 Lauric Spermaceti, cinnamon, palm
o Glycolipids (glycosphingolipids): Lipids + fatty kernek, coconut oil, laurels, butter
acid, sphingosine + carbohydrate 14 Myristric Nutmeg, palm kernel, coconut
- Imp. in nervous tissue such as brain. oils, myrtles, butter
- glycocalyx – found in outer leaflet of the plasma 16 Palmitic Animal and plant fats (end
membrane product of mammalian FA
- glycosphingolipids- major glycolipids found in animal synthesis)
tissues, contain ceramide and one or more sugars. 18 Stearic
- Galactosylceramide - major glycosphingolipid of
brain. It contains a number of characteristic C24
B. UNSATURATED FATTY ACIDS
fatty acids, eg: cerebronic acid
- contain one or more double bonds
o Other complex lipids: Lipids such as sulfolipids, - geometric isomerism can occur, don’t allow rotation.
amino lipids and Lipoproteins o Cis - acyl chains are on the same side of the
bond, oleic acid
- Most unsat FA, being “bent” 120 at the double bond
3. Precursor and derived lipids: fatty acids, glycerol, steroids,
➢ Arachidonic acid, with four cis double bonds, is
other alcohols, fatty aldehydes, ketone bodies, hydrocarbons,
bent into a U shape
lipid-soluble vitamins and micronutrients, and hormones
o Trans – opposite side, elaidic acid
- Neutral Lipids: uncharged, acylglycerols (glycerides),
- alter these spatial relationships, present in foods ads
cholesterol, and cholesteryl esters
byproduct of saturation of FAs during hydrogenation
(margarine)
V. FATTY ACIDS - Consumption can lead to DM or CVD
- Aliphatic/ long chain of carboxylic acids
- Usually contains even number of C- atoms, saturated 1. Monounsaturated - one double bond (monoethenoid,
or unsaturated monoenoic) acids
- occurs in the body mainly as esters but are found 2. Polyunsaturated - two or more double bonds
unesterified in the form of free fatty acids (a transport (polyethenoid, polyenoic) acid
form in the plasma). 3. Eicosanoids - derived from eicosa (20-carbon) polyenoic
- free fatty acids – unesterified fatty acid fatty acid
➢ prostanoids (prostaglandins (PGs), prostacyclins
(PGIs), and thromboxanes (TXs)
A. SATURATED FATTY ACIDS
a. Prostaglandins – local hormone, resp. for
- no double bond inflammatory response, synthesized in vivo
- Isolated from plants and animal sources by cyclization of the center of the carbon chain of 20-
- Low temp : C-chain forms zigzag carbon (eicosanoic) polyunsaturated FA (eg,
- At High temp: some bonds rotate, causing chain arachidonic acid) to form a cyclopentane ring
shortening b. Thromboxanes - have the cyclopentane ring
- Follows the Geneva System for naming: interrupted with an oxygen atom (oxane ring)
➢ saturated acids end in –anoic - facilitates blood clot formation, vasoconstrictor,
➢ Carbon atoms are numbered from the carboxyl and a potent hypertensive agent
carbon (C -#1).
➢ C#2 – alpha ; C#3 – beta ; C#4 – gamma
➢ terminal methyl carbon - omega or n-carbon.

Trans # 9 Bacud 2 of 4
 ➢ leukotrienes (LTs), and lipoxins (LXs). 20:5; ɷ6 Arachido All cis – Precursor
c. leukotrienes and lipoxins - formed via the 5,8,11,14,17 nic 5,8,11,14 of PGs,
lipoxygenase pathway 20:4 ; eicosatetrae derived
- Melting point: inc. with chain length; dec. according to 5,6,11,14 noic from
unsaturation linoleic
acid
Omega FA others
- Long cgain Omega 3 Fas – has anti- inflamatory 20: 5; ɷ3 Timnodo all-cis- all-cis-
effects → promotes synthesis of PGs and LTs 8,11,14,17 nic 5,8,11,14,1 4,7,10,13,
- α-linolenic acid (ALA) – plant oils 7- 16,19-
Eicosapent Docosahe
- eicosapentaenoic acid (EPA) – fish oil
aenoic xaenoic
- docosahexaenoic acid (DHA) – fish and algae oil
22:6;4,7,10, ɷ3 Cervonic all-cis- Fish oils,
13,16,19 4,7,10,13,1 algal oils,
UNSATURATED FAs
6,19- phospholi
# of C, # & Fa- Common Systemic Occurre- Docosahex pids in
position of m Name Name nce aenoic brain
Double Bond
Monoenoic acids
Dietary Fatty Acids
16: 1 ; 9 ɷ 7 Palmitolei Cis – 9 – All fats
c Hexadecen
Trans FA By product of saturation of FA during
oic
hydrogenation or “hardening” of natural
18: 1;9 ɷ9 Oleic Cis – 9 - Most
oils in manufacture of margarine
Octadeceno common,
↑ cor.heart dse and DM
ic olive oil
Saturated FA ↑ cor.heart dse, ↑ risk of prostate and
18: 1; 9 ɷ9 Elaidic Trans – 9 – Hydrogen
colon ca
Octadeceno ated and
ic ruminant ɷ 3 FA -Anti- inflammatory
fats -suppress arrhythmia, ↓ serum TAGs,
Dienoic acid tendency for thrombosis and BP
↓ cor. heart dse, sudden cardiac death
18:2 ; 9, 12 ɷ6 Linoleic All cis- 9, Essential
12- FA ɷ 6 FA -provide arachidonic acid
octadecadie Corn, ↓ cor. heart dse
noic peanut,
cottonsee VI. TRIACYLGLYCEROL (TRIGLYCERIDES)
d,
soybean - Esters of the trihydric alcohol glycerol and FA
Trienoic acid - Main storage form of fatty acids
18:3; 6,9,12 ɷ6 γ- All cis – Eveprim, - solid at body temp, whereas if the fatty acid residues
Linolenic 6,9,12 borage are polyunsaturated, it is liquid to below 0°C.
Octadecatri oil, minor - Membrane lipids, must be fluid at all environmental
enoic FA in temperatures, are more unsaturated than storage
animals lipids.
18:3: 9,12, ɷ3 α- All cis- 9,12, Essential - Lipids in tissues that are subject to cooling, for
15 Linoleic 15 FA example, in hibernators or in the extremities of
Pctadecatri Frequentl animals, are also more unsaturated.
onoic y w/
linoleic VII. AMPHIPATHIC LIPIDS
acid but
▪ partly hydrophobic ( water insoluble) partly
particularl
hydrophilic ( water soluble)
y in
▪ Micelles- formed when a critical conc. Of
linseed oil
amphiphatic lipids is present in an aqueous medium.
Tetranoic acid

Trans # 9 Bacud 3 of 4
 ▪ Liposomes – formed by sonicating an amphipathic ▪ Plant derived polyprenoids: rubber, camphor
lipid in an aqueous medium vitamins A, D, E, K, and β-carotene
▪ Emulsions -larger particles, formed by nonpolar
lipids in an aqueous medium.
X. LIPID PEROXIDATION
- These are stabilized by emulsifying agents such as
amphipathic lipids (eg, phosphatidylcholine), which Peroxidation (auto-oxidation)
form a surface layer separating the main bulk of the - responsible for deterioration of foods (rancidity)
nonpolar material from the aqueous phase ▪ Free radicals: causes damage to tissues in vivo,
cause of cancer, inflammatory diseases,
VIII. CLINICAL CORRELATION atherosclerosis, and aging
- vitamin E (tocopherol) – natural anti-oxidants
1. LIPID MALALBSORPTION - preventive antioxidants- reduce the rate
▪ Manifested: as steatorrhea of chain initiation
▪ Causes: liver dse, pancreatic dse,
- chain-breaking antioxidants - interfere with chain
choleithiasis, shortened bowel, intestinal
propagation.
mucosal defects (Corrs Dse)
▪ Result: deficiency in vit. A,D,E,K and
essential FA X. REFERENCES
2. ESSENTIAL FA DEFICIENCY • Dr. Loluquisen’s lecture
▪ Results in: ichthyosis (scaly dermatitis), hair • Rodwell, V.W. et. al (2015). Harper’s Illustrated
loss, poor wound healing, visual and Biochemistry 31st ed.
neurologic abnormalities
3. CARNITINE DEFICIENCY
▪ Cause: inadequate synthesis of renal loss of
carnitine
▪ Presentation: Hypoglycemia and lipoid
accumulation with muscular weakness
▪ Treatment: oral supplementation
4. Others
▪ Jamaican vomiting sickness
▪ Refsum dse
▪ Zellweger syndrome
▪ Adrenoleukodystrophy

IX. IMPORTANT TO KNOW

▪ Gangliosides - derived from glucosylceramide that
contain in addition one or more molecules of a sialic
acid
- fnx in cell-cell recognition, communication
and as receptors for hormones and bacterial
toxins such as cholera toxin
▪ Neuraminic acid- is the principal sialic acid found in
human tissues.
▪ GM3 – 1 ceramide +1 glucose + galactose + NeuAc
▪ GM1 - receptor in human intestine for cholera toxin
▪ Cholesterol- precursor of bile acids, ACTH, sex
hormones, vitamin D, and cardiac glycosides
- major constituent of plasma membrane and
lipoprotein
▪ Ergosterol – precursor of Vit D
▪ Polyprenoids – not steroids but they, too, are
synthesized from 5C isoprene units
▪ Ubiquinone – respiratory chain
▪ Dolichol – glycoprotein synthesis
Trans # 9 Bacud 4 of 4