11/20/17

CHAPTER 13: Lipids: Structure and Function

LIPIDS ARE A DIVERSE CLASS OF MOLECULES

• Lipids include any biological compounds that are
insoluble in water and can dissolve in nonpolar
organic solvents.
• Lipids are highly diverse in both
Triacylglycerides
function & structure:
1. Triglycerides (energy storage) Phospholipids

2. Phospholipids & glycolipids

(membrane structure)
Sterols
3. Sterols (cholesterol & steroids)
4. Eicosanoids (inflammation & Eisosanoids
pain)

CHAPTER 13: Lipids: Structure and Function

OTHER BIOLOGICALLY IMPORTANT LIPIDS

Lipids serve important functional roles at the tissue
and organism levels:
• Pigments
Ø Color of tomatoes, carrots, pumpkins, some birds

• Waxes (from algae & insects)

Ø Waxes are lipids used to store energy (“bug fat”)
• Secreted oils (water repellents)
Ø Prevents excessive wetting of skin (wet climate)
Ø Prevents excessive evaporation (dry climate)
• Fat-soluble vitamins
Ø Antioxidants (Vitamin E)
Ø Blood clotting (Vitamin K)
Ø Electron transfer (Coenzyme Q)

CHAPTER 13: Lipids: Structure and Function

CLASSIFICATION OF LIPIDS
• Lipids are typically classified according to
differences in their structure & biological function:
• Two major structural classes of lipids:
1. Lipids that contain or are derived from fatty acids
a) Energy storage lipids (triglycerides)
Functional
b) Structural lipids (membrane lipids)
subclasses:
c) Signaling lipids (eicosanoids)

2. Lipids that are not associated with fatty acids:

Functional a) Sterols (cholesterol & steroid hormones)
subclasses: b) Vitamins

1
 11/20/17

CHAPTER 13: Lipids: Structure and Function

OUTLINE

• 13.1 Energy Storage Lipids: Triglycerides

• 13.3 Fatty Acid Catabolism

• 13.2 Membrane Lipids: Phospholipids and

Glycolipids

• 13.4 Cholesterol and Other Steroid Hormones

CHAPTER 13: Lipids: Structure and Function

FATTY ACID STRUCTURES

• Fatty acids are long-chain hydrocarbons that end
with a carboxylic acid:
Ø Typically 12-20 carbons in length
Ø Naturally occurring fatty acids
have an even number of carbons
(due to their synthetic route)

• Fatty acids can be saturated or unsaturated:

Ø Saturated fatty acids are alkanes (all C-C bonds)
Ø Unsaturated fatty acids are alkenes (have 1 or more
C=C double bonds)
Ø Polyunsaturated fatty acids have multiple C=C bonds

CHAPTER 13: Lipids: Structure and Function

FATTY ACID CARBON NUMBERING

• Two nomenclature systems are used to identify the
length & double bonds in fatty acids:
1. The delta system (blue)
Ø The carbonyl carbon is designated as #1 carbon
Ø double bonds specified with a ∆ symbol followed by the
superscripted number of the first carbon in the double bond

2. The omega system (pink)

Ø begins numbering with the carbon at the end of
the chain (ω-1)
Ø double bonds are specified relative to end carbon

Example: Linoleic acid

Delta system: 18:2 ∆9,12
Omega system: 18:2 ω-6

2
 11/20/17

CHAPTER 13: Lipids: Structure and Function

MELTING POINTS OF FATTY ACIDS

• Fatty acids are primarily nonpolar molecules:
Ø Primarily interact by dispersion forces between the
hydrocarbon chains
Ø The more contacts between these chains, the higher
the melting point of fatty acids

• Two things impact melting points:

1. Hydrocarbon chain length
More carbons = more interactions

2. C=C double bonds

“cis” bond kinks decrease interactions
so unsaturated fatty acids have lower MP

CHAPTER 13: Lipids: Structure and Function

UNDERSTANDING UNSATURATION
• Naturally occurring fatty acids may be saturated or
unsaturated:
Ø Animal fats contain more saturated fatty acids (ex: butter)
Ø Plant oils are unsaturated fatty acids (ex: cooking oils)

• Naturally unsaturated
fatty acids always
contain cis C=C bonds:
Ø Trans fats are a by-
product of industrially
processed plant oils
Ø Have properties between
those of natural fatty acids

CHAPTER 13: Lipids: Structure and Function

TRIGLYCERIDES: ENERGY STORING LIPIDS

• The most important class of energy storage lipids
are triacylglycerols (aka. triglycerides or “fat”):
• The name describes structure:
Ø Tri = three
Ø Acyl = carbonyl-containing hydrocarbon
Ø Glycerol = 3-carbon tri-alcohol

Remember
HOW fatty
acids are
connected to
the glycerol
“backbone”

3
 11/20/17

General, Organic, and Biochemistry Chapter 6

FATTY ACID COMPOSITION IN TRIGLYCERIDES

• Triglycerides may contain a variety of fatty acids:
Ø Animal fats are semi-solid, composed mostly of
saturated fatty acids (eg. palmitic)
Ø Plant oils are liquid, and contain mostly unsaturated
fatty acids (eg. linolenic acid)

CHAPTER 13: Lipids: Structure and Function

THE SATFAT GRAPH

• The graph below indicates the composition of fatty
acids in a wide variety of common triglycerides

• Which of these
contain more
energy per fatty
acid...and why?

• Which of these are

“healthier” for you
to use in cooking?

CHAPTER 13: Lipids: Structure and Function

FATTY ACIDS AND INFLAMMATION

• Arachidonic acid is an important polyunsaturated
fatty acid (20:4Δ5,8,11,14) for production of eicosanoids:

Ø Eicosanoids are lipids

involved in the regulation
of inflammation, pain,
blood clotting & muscle
contraction

• Non-steroidal anti-inflammatory drugs (NSAIDs)

inhibit the enzymes that produce some eicosanoids:
Ø Ibuprofen, aspirin, and naproxen are all in this class
Ø Used to decrease aspects of inflammation such as fever,
pain, itching, and swelling

4
 11/20/17

CHAPTER 13: Lipids: Structure and Function

PRACTICE PROBLEMS
1. Which vegetable oils are high in saturated fat and
should, therefore, be included in limited amounts
in the diet?
2. Are most unsaturated fats obtained from
vegetable or animal sources?
3. Which product is healthier: coconut oil or canola
oil? Explain.
4. Why does arachidonic acid have a lower melting
point than linolenic acid, even though it has two
more carbon atoms in its chemical formula?

CHAPTER 13: Lipids: Structure and Function

WHY STORE ENERGY IN FAT?

D-glucose
• For some tissues (liver and heart),
fatty acids provide most of the energy
needs for cells
• Saturated fats provide more energy 3.7 Cal/gram
density than carbohydrates: Stearic acid

1. Fatty acids carry more energy per carbon

because they are more reduced
2. Fatty acids carry less water per gram
because they are nonpolar (higher density)

Fats are more efficient energy

storage molecules 9.6 Cal/gram

CHAPTER 13: Lipids: Structure and Function

STAGES IN LIPID CATABOLISM

1. Stage 1: Triglycerides are
hydrolyzed into glycerol and
fatty acids.

2. Stage 2: Fatty acids are

oxidized to acetyl CoA.

3. Stage 3: Acetyl CoA is

converted into ATP energy
and CO2 via citric acid cycle
and oxidative phosphorylation.

5
 11/20/17

CHAPTER 13: Lipids: Structure and Function

STAGE 1: TRIGLYCERIDE HYDROLYSIS

• Dietary triglycerides are initially present as fat
globules which must be partially digested prior to
absorption in the small intestine: Liver Stomach

Ø Bile salts (from liver) act as Small

Gall
natural detergents that produce bladder intestine

fine droplets of solubilized fat. Large

intestine

• Fatty acids are released from the

glycerol backbone by enzymes called lipases:

CHAPTER 13: Lipids: Structure and Function

LIPID TRANSPORT
• Because lipids are insoluble in water, they must be
packaged in forms to allow transport in the blood
• Lipoproteins are lipid transport particles:
Ø Spherical particles with a
lipid core of fatty acids &
cholesterol
Ø Covered with a single
membrane layer
Ø Decorated with proteins
that target the particles to
specific cell types for
uptake & catabolism

CHAPTER 13: Lipids: Structure and Function

LIPOPROTEIN CATEGORIES
• The categories of lipoproteins are based on density:
Ø Proteins have much greater density than lipids
Ø Density is a reflection of lipid/protein ratios

Higher density
is better!

“Bad”
cholesterol

“Good”
cholesterol

6
 11/20/17

CHAPTER 13: Lipids: Structure and Function

STAGE 2: FATTY ACID OXIDATION

• Fatty acid oxidation takes place in the
mitochondrial matrix:
Ø Same location as the
citric acid cycle
Ø Products feed into the
citric acid cycle &
electron transport chain

• In several steps, the oxidation of fatty acids

produces acetyl CoA, NADH, and FADH2.
Ø Steps occur in cycles removing 2 carbon units per cycle

CHAPTER 13: Lipids: Structure and Function

FATTY ACID ACTIVATION

• Import of fatty acids into the mitochondria prior to
catabolism requires that they first be “activated”
• Activation involves the formation of an acyl CoA, a
thioester similar to acetyl CoA:
Ø Enzymatic condensation reaction (acyl CoA synthase)
Ø Requires energy from ATP to make thioester

Note the cost: -2 ATP

To mitochondrial
equivalents are “invested”
matrix

CHAPTER 13: Lipids: Structure and Function

b-OXIDATION
• b-oxidation is a cycle of four reactions that are
repeated many times to break down the fatty acid
down by two carbons at a time:

Ø The oxidation steps Acyl-CoA

occur at the third carbon

(the b-carbon)
Ø Each cycle produces 2
carbon units as acetyl-
CoA at each cycle

7
 11/20/17

CHAPTER 13: Lipids: Structure and Function

SUMMARY OF b-OXIDATION
1. The alkane acyl chain is
oxidized to an alkene
intermediate using FAD
2. The C=C double bond is
hydrated to a secondary
alcohol
3. The secondary alcohol is
oxidized to a ketone using
NAD+
4. Acyl chain transfer to a
new CoA-SH, while acetyl-
CoA is removed

CHAPTER 13: Lipids: Structure and Function

ENERGY YIELD IN b-OXIDATION

The products of b-oxidation are energy-rich!!!
• A saturated, 16-carbon fatty acid (palmitate)
produces the following in 7 cycles:
1. 8 two-carbon acetyl CoA units à to citric acid cycle
2. 7 FADH2 molecules to electron
3. 7 NADH molecules transport chain

The number of b-oxidation cycles is half the total

number of carbon atoms minus one, because the
last step produces two acetyl CoA molecules
(a four-carbon chain split into two).

CHAPTER 13: Lipids: Structure and Function

ENERGY ACCOUNTING IN b-OXIDATION

The ATP yield from one palmitic acid (C-16:0) is:

Activated palmitoyl-CoA

1. Initial activation of palmitic acid = -2 ATP

2. 8 acetyl CoA molecules x 10 ATP = 80 ATP
3. 7 FADH2 molecules x 1.5 ATP = 10.5 ATP
4. 7 NADH molecules x 2.5 ATP = 17.5 ATP
Total 106 ATP
Note: this number differs from textbook due to
estimated yields from FADH2 & NADH

8
 11/20/17

CHAPTER 13: Lipids: Structure and Function

PRACTICE PROBLEMS
1. What are the two kinds of oxidation that occur in
each cycle of b-oxidation?

2. Calculate the number of ATP molecules produced

from complete catabolism of stearic acid (18:0).

3. What would happen to ATP yield if a single C=C

double bond were added to stearic acid to make
oleic acid (18:1D9)?

CHAPTER 13: Lipids: Structure and Function

CELL MEMBRANE FUNCTION

• The cell membrane is a semi-permeable structure
that defines the boundaries of all cell types:
Fluid mosaic model
Ø It is composed of lipids,
proteins & carbohydrates
Ø Semi-fluid composition
allows lateral diffusion

• The cell membrane has many roles:

1. Controlling flow of ions into and out of cells
2. Uptake of nutrients and disposal of waste
3. Cell recognition and communication

CHAPTER 13: Lipids: Structure and Function

CELL MEMBRANE COMPOSITION

• The central structural component of membranes is
its different lipids, which include:
1. Phospholipids
Ø Major membrane component
Ø Fatty acids with a phospodiester attached along with
some other polar “head group”
2. Glycolipids
Ø Fatty acids covalently attached to a carbohydrate
3. Cholesterol
Ø Non-fatty acid lipid component of membrane

9
 11/20/17

CHAPTER 13: Lipids: Structure and Function

TYPES OF MEMBRANE LIPIDS

Fatty-acid containing lipids

Sterols
(no fatty acids)

Glycerophospholipids Sphingomyelins Sphingolipids

CHAPTER 13: Lipids: Structure and Function

TWO BACKBONES FOR MEMBRANE LIPIDS

• Membrane lipids can be linked to fatty acids by two
different types of “backbones”:
Ø Glycerol = simple 3-carbon, tri-alcohol
Ø Sphingosine = more complex hydrocarbon:
§ Two alcohols
Note the cartoon
§ Amine designations for
§ Long-chain alkene each backbone

CHAPTER 13: Lipids: Structure and Function

GLYCEROPHOSPHOLIPID STRUCTURES
Cartoon Structure Components:
1. Glycerol backbone (like triglycerides)
2. Two fatty acid chains
3. Phosphoryl group (phosphodiester)
4. Amino alcohol head group

Fatty acids are attached

by ester bonds

10
 11/20/17

CHAPTER 13: Lipids: Structure and Function

SPHINGOLIPID STRUCTURES
Cartoon Structure Components:
1. Sphingosine backbone
2. One fatty acid chain
3. Phosphoryl group (phosphodiester)
4. Amino alcohol head group

Fatty acid are attached

by an amide bond

CHAPTER 13: Lipids: Structure and Function

AMINO ALCOHOL HEAD GROUPS

• The amino alcohol “head group” associated with
phospholipids varies in structure & charge:
Ø ethanolamine +1
Ø choline
Ø serine +1
• The head groups vary
in terms of their charge
at physiological pH 0

CHAPTER 13: Lipids: Structure and Function

GLYCOLIPID STRUCTURES
Cartoon Structure Components:
1. Sphingosine backbone
2. One fatty acid chain
3. Carbohydrate head group

Fatty acid are attached

by an amide bond

11
 11/20/17

CHAPTER 13: Lipids: Structure and Function

MEMBRANE LIPIDS ARE AMPHIPATHIC

• Amphipathic compounds contain both
polar regions and nonpolar regions:
Ø The polar regions of membrane lipids
contain charged phosphate & head group
Ø The nonpolar region is the hydrocarbon
chains of the fatty acid “tails”

Amphipathic
membrane lipids
contain one polar
“head” and two
nonpolar “tails.”

CHAPTER 13: Lipids: Structure and Function

CELL MEMRANE STRUCTURE

• Cell membranes consist of two layers of
amphipathic lipid, termed a lipid bilayer:
Ø Layers are aligned so that the polar heads are in
contact with water inside & outside the cell
Ø Nonpolar tails form an internal hydrophobic
environment not in contact with water

Other nonpolar
molecules—such
as cholesterol—
are embedded
within the lipid part
of the bilayer

CHAPTER 13: Lipids: Structure and Function

STEROLS
• Sterols are compounds derived from cholesterol
that contain a basic 4-ring system:

• Cholesterol is found in
animal cell membranes:
Ø Acts as a “buffer” for
membrane fluidity
Ø Used as a precursor for
other key sterols

12
 11/20/17

CHAPTER 13: Lipids: Structure and Function

BILE ACIDS
• Bile acids are amphipathic molecules that are
used in the digestion of dietary lipids:
Ø Made in the liver and stored in the gall bladder
Ø Released into the intestine after a meal rich in fats

Cholesterol Cholate (a bile salt)

What are the key chemical differences

between these molecules?

CHAPTER 13: Lipids: Structure and Function

VITAMIN D3
• Vitamin D3 is formed by the action of sunlight on
cholesterol derivatives in the skin:
Ø The ultraviolet (UV) wavelengths cause ring opening
Ø Vitamin D3 is a hormone that is required for the uptake
of dietary calcium ions

UV light

Cholesterol
Vitamin D3

CHAPTER 13: Lipids: Structure and Function

STEROID HORMONE FUNCTION

• Cholesterol is the starting point for the
biosynthesis of the 5 steroid hormone classes:

• Adrenal steroids:
Ø Include the glucocorticoids and mineralocorticoids
Ø Regulate metabolism, immune system activity & ion balance

• Sex steroids (gonadal hormones):

Ø Include the progestins, estrogens, and androgens
Ø Regulate reproductive processes

13