Biological Roles of Lipids

Energy Storage Cell compartmentalization Water Repellent

Waterproof feathers, fur,

wool, skin.
Adipose tissue Prevent water loss in plants
Insulation Lipids Light absorption
Biomolecules which are
not soluble in water
Retinal – vision
Blubber, subcutaneous fat
Chlorophyll - photosynthesis
Cell/Tissue
signaling Enzyme cofactor Antioxidants Pigments/color
melanin
Vitamin K Vitamin E

Carotene
Phosphatidylinositol pathway Skin, hair, eye, feather,
Hormones e.g. testosterone Ubiquinone/coenzyme Q10 flower, leaf color
 Class Topics

• Function of lipids
• Type of lipids
• Fatty acids & nomenclature
• Triacylglycerols
• Phospholipids
• Sphingolipids
• Other types of lipids
 Types of Lipids
Fatty Acids

Triglycerides Membrane Lipids Sterols

Phospholipids
Galactolipids
Sulfolipids
Sphingolipids Cholesterol
(Isoprene derivative)

Eicosanoids Isoprene derivatives Polyketides

Paracrine hormones
e.g. Prostaglandins (PG)
Thromboxanes
Leukotrienes
(derived from fatty acid)
e.g. Vitamins Secondary metabolites
Plant scents e.g. erythromycin (antibiotics)
Dolichols Amphotericin B (antifugal)
steroids Lovastatin (inhibitors of
Quinones cholesterol biosynthesis)
 Fatty Acids
Hydrocarbon chains that end with a carboxylic acid group
Saturated
3 5 7 9 11 13 15

2 4 6 8 10 12 14
16
Hexadecanoic acid Palmitic acid (16:0)

Unsaturated 7 9
3 5 11 13 15

2 4 6 8 10 12 14
All-trans-∆6,∆10,∆14-Hexadecatrienoic acid

Have variable length

Have different degrees of unsaturation (double bond)
Monounsaturated = one double bond, polyunsaturated = two or more double bonds
Numbered from carbon of carboxylic acid
Have common name and systematic name
 Fatty Acids - Nomenclature
Exam Hint: You will be asked to draw a fatty acid from its systematic name

Unsaturated 7 9
3 5 11 13 15

2 4 6 8 10 12 14 16

All-trans-∆6,∆10,∆14-Hexadecatrienoic acid
Hexadeca(n) = 16 carbons
Tri(en) = 3 double bond
-oic acid --> it has a carboxylic group

All-trans-∆2,∆4-hexadienoic acid Trans-∆5,- pentenoic acid

IUPAC numerical multiplier

 Fatty Acids – Cis vs. Trans

Stearic Acid

Trans-∆11-Octadecenoic acid

Oleic Acid

Cis-∆9-octadecenoic acid
Fatty Acids - Nomenclature

Which fatty acid is this?

 Fatty Acids – Omega (w)

a-carbon w-carbon

Third bond
from w-
carbon is cis

Sixth bond
from w-
carbon is cis
 Fatty Acids - Properties

Solubility
Decreases as chain length increases
Melting point
Decreases as chains become shorter
Decreases as number of double bonds increase
Less energy is needed to disrupt the disordered packing
of unsaturated fatty acids
 Fatty Acids - Waxes
Waxes are esters of long-chain saturated and unsaturated
fatty acids with long-chain alcohols

Beeswax Spermaceti
Found in head of
melting point
sperm whale
62-65 °C

Cetyl palmitate
Ester of palmitic acid and cetyl alcohol
Melting point 46 -50°C

Plant Cuticle Wax Lanolin – wool wax

e.g. Carnauba wax Composition variable
From Brazilian pines
Melting point 82–86 °C Wax excreted from
sebaceous glands of
Uses: car polish, sheep. It soaks into
floor polish, sweet the wool keeping the
coating fleece waterproof
 Triglyceride
Three fatty acids joined to a glycerol via ester bonds

• Proper name = Triacylglycerol

• Energy storage – located in adipose tissues
• Transport in blood via low density lipoproteins (LDL) and high density lipoproteins (HDL)
• Also found in free form in blood. Too much = cardiac disease, arteriosclerosis
 Membrane Lipids
Lipid composition of biological membranes

Diacylglycerol Ceramide Schematic

Parent – base biomolecule representation
 Glycerophospholipids
Glycerol molecule with two fatty acids and a phosphate group
Hydrophilic
Hydrophobic

Phosphate group binds to an amino or alcohol group (X-group)

The X-group gives the glycerophospholipid its name and properties
 The X-groups of Glycerophospholipids
Head groups have
different sizes and
PA charges

PE Each type of biological

PC membrane has a
particular lipid
PS composition and
overall charge
PG
The charge and
composition of a
PI membrane affects the
membrane’s
properties, its
CL curvature, the function
of proteins in the
membrane, and which
proteins bind to the
membrane
 Phosphoinositide Signaling Cascades

• PI can be phosphorylated (usually by a kinase in response to a cell stimulus)

• Phosphorylated PI can be cleaved by phospholipase C generating DAG and IP x
• DAG is membrane bound and activates protein kinase C if Ca2+ is present
• IPx cell signaling molecule which activates other proteins including Ca2+ channels
• Example: Insulin deactivation of glycogen phosphorylase a involves PIP signaling
cascade
Insulin Inhibition of Glycogen Phosphorylase

Take home message: Insulin inhibition of glycogen phosphorylase

involves PI signaling pathway
 Glactolipids & Sulfolipids
Found mainly in plants as phosphate is a limited resource
Glactolipid

Contains one
or more
sugar groups
Sulfolipid

Contains a
sulfate group
And a sugar
group
 Sphingolipids
Consists of one sphingosine molecule attached to a fatty acid
via an amide linkage and to an R-group

Sphingolipids do not contain glycerol but C1, C2 and C3 are

functional equivalents

Ceramide (sphingolipid without an R-group) is the parent of

all sphingolipids and is equivalent to DAG of
glycerophospholipids
 Sphingolipid R-goups

Sialic acid

Gangliosides
Phospholipid Often in outer leaflet R-group complex
Common in myelin of cell membrane
Negative charge due
Neutral – no charge to sialic acid
R-group often choline
or Define blood group
Cell recognition
Phosphoethanolamine
 Membrane Formation
• Phospholipids and Glycolipids are amphipathic.
• Hydrophobic portion clusters together to avoid H2O
 Sterols
Characteristic structure
consists of four fused rings:
three six carbon,
one five carbon.

Steroid nucleus is almost

planar and relatively rigid

Cholesterol is major
sterol of animal tissue –
has a polar head group
and hydrocarbon side
group (from c17)

Stigmasterol is a sterol of plants

Ergosterol is a sterol of fungi

Cholesterol, stigmasterol and ergosterol are all components of biological membranes

Sterols as Signaling Molecules
 Other Signaling Molecules
Eicosanoids = paracrine hormones

• Derived from the fatty acid arachidonate (All-cis ∆5∆8∆11∆14 eicosatetraenoate)

• Act on cells near the point of hormone synthesis (paracrine signalling)
• Prostaglandins stimulate smooth muscle contraction, affect blood flow, modulates
wake-sleep cycle, elevates body temperature, cause inflammation and pain
• Thromboxanes are produced by platelets. They reduce blood flow and stimulate
blood clotting
• Leukotrienes found in leukocytes, simulated pulmonary smooth muscle contractions
 Isoprene Derivatives
Fragrances Pigments/Color

Zeaxanthin (bright yellow)

Canthaxanthin (bright red)

Isoprene
Attract/repell insects Color leaves, fruit, feathers

Steroids Enzyme Co-factors

Vitamin K
(Blood clotting)
Ubiquinone/coenzyme Q10

Vitamin E
(Antioxidant) Retinol
 Polyketides
• Secondary metabolites produced by certain living organisms to increase survival
chances
• Usually biosynthesized through the decarboxylative condensation of malonyl-CoA
derived extender units
• Tend to be antibiotics, antifungals, antiparasitics, insecticides, anticholesteremic

Amphotericin B (antifungal)

Erythromycin
(antibiotic)

Lovastatin (statin)
What You Need to Know for Midterm #1

• Know the different types of lipids and their role in

biology
• Be able to draw a fatty acid from systematic name
• Be able to draw the different types of phospholipids
and glycolipids in schematic representation and
describe the differences
• Draw the structure of cholesterol, testosterone,
estradiol and squalene
• Recognize an isoprene unit
 Practice Problems

Write out the systematic name for each of these fatty acids
IUPAC numerical multiplier
 Homework

Reading:

Lehninger: Chapter 10: 10.1-10.3

Practice Problems:
Lehninger: Chapter 10, Q:1-5, 8-10, 13-14

Sapling: Ch 10: Reading quiz

Ch 10: Drawing and Modifying Lipid Structures
Ch 10: Lipids
 Office Hours
Thursday: 11:00 – 12:00 pm
Friday: 1:30 – 2:30 pm

458, Donner Lab