9/5/13

Lipids and membrane:

Not all fats are bad
Becker’s Ch 3: 65-70
Becker’s Ch 7: 156-178

Veronica R. Moorman, Ph.D. moormanr@sas.upenn.edu

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Lipids and membranes outline

•  Definition of lipids
•  Types of lipids
•  Lipids in membranes
•  Proteins in membranes

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Lipids are hydrophobic macromolecules

that are NOT formed by polymerization.
•  Sometimes not even considered macromolecules
•  Some are amphipathic (both hydrophobic and hydrophilic)
•  Variety of functions
–  Energy storage
–  Membrane structure
–  Enzyme cofactors
–  Hormones
–  Membrane anchors for proteins Fig 2-11. Becker’s World of the Cell, 8 th ed. Hardin, et al. © 2012 Pearson.

–  Signaling messengers
–  Electron carriers
–  Pigments (photosynthesis and vision)
–  Emulsifier agents (digestion and blood transport)

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Lipids can be divided into six classes based

on their structure.
1.  Fatty acids (FAs) 1

2.  Triacylglycerols
Built from FAs
3.  Phospholipids 2 3

4.  Glycolipids
5.  Steroids
6.  Terpenes
4 5 6

Fig 3-27. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.
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Storage lipids and some structural lipids are

chemical derivatives of fatty acids.
FAs are long, amphipathic molecules containing an HEAD
unbranched hydrocarbon chain with a carboxyl group
at one end
Saturated FAs Unsaturated FAs

4-36 Cs (even # only)

•  All single bonds •  Some double bonds TAIL
•  Relatively straight •  “Kinked” shape
•  Packs together well •  Does not pack together well

Can release large amounts of energy

Fig 3-27. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson. Fig 3-21. Life, 10th ed. Sadava, et al. © 2014 W.H. Freeman.

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Trans unsaturated fats are rare in nature

and do not produce a kink in the structure.
H H H

Cis Trans
Trans unsaturated fatty
acids are linked to an
increased risk of heart
disease and elevated
cholesterol levels

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The physical properties of FAs change their

water solubility and melting temperature.
Water solubility Melting temperature
Largely insoluble (from tails);
some solubility (from heads)
•  Less soluble with:
–  Longer tails
–  More double-bonds

How can they be soluble at all?

(cis)

Unsaturated trans-FAs melt more similar to saturated FAs.

Fig 7-13. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Comparing oleic acid, elaidic acid, and stearic

acid show us differences in properties.
All three have 18 carbons tails

Structure.:

Name.:
(elaidic acid)
Melting temp.: 152-161 ºF 55-57 ºF 107-111 ºF
Water solubility (at 73 ºF): 0.1-1 g/100 mL Negligible ~1 g/100mL

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Triacylglycerols (triglycerides) are storage lipids,

made of a glycerol with three FAs attached.
Condensation/dehyration reactions
3 carbons (each
with hydroxyl)

Fig 3-27. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

H O H H H H H H H
H H H H H H H H
H C O C C C C C C C C H
C C C C C C C C
H H H H H H H
H H H H H H H H

H C O
O
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
Simple triglycerides: 3 FA are identical
C C C C C C C C
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
Complex triglycerides: FAs are not the same
O H H H H H H H
H H H H H H H H
H C O C C C C C C C C H
C C C C C C C C
H H H H H H H H
H H H H H H H H

Fig 5-11. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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Phosphoglycerides are hydrophobic, having

hydrophilic heads and hydrophobic tails.
Hydrophilic head
Hydrophobic tails
Hydrophilic head

CH2 +
N(CH ) 3 3 Choline Choline
CH2
O
O P O– Phosphate Phosphate
O
CH2 CH CH2
Glycerol Glycerol
O O
C O C O
Typical
Hydrophobic tails

phosphlycerides have
one unsaturated and
one saturated chain Fatty acids Fatty acids

Physical properties
are affected by length
and saturation of FAs Fig 5-13. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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Phospholipids can form membrane

bilayers or other structures in water.

WATER WATER
Hydrophilic heads

Hydrophobic tails

Phospholipid Hydrophobic tails

bilayer
Hydrophilic heads
WATER

Fig 5-14. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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The fluid mosaic model describes a phospholipid

bilayer with proteins dispersed throughout.

•  Lipids in each monolayer are in

constant motion
Hydrophobic region
of integral membrane protein •  Proteins are also able to move
laterally within the membrane,
though some are anchored to
internal structural elements
•  Lipid rafts are membrane
microdomains enriched in
cholesterol and
glycospingolipids, more ordered
Hydrophobic region of integral membrane protein
Phospholipid bilayer
than the surrounding and often
containing many signaling
Fig 7-3. Biology, 7th ed. Campbell and Reece. © 2005 Pearson. proteins

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The fatty acids in phospholipids and glycolipids are

essential to membrane structure and function.
•  Typically 12-20 carbons long
–  Barrier to polar molecule diffusion
–  Dictates the thickness of membrane (6-8 nm)
•  Saturation levels affect fluidity and melting temperature

Fig 7-12. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson. Fig 7-5. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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Membrane fluidity is influenced by ridged,

bulky sterols that act as a fluidity buffer.
•  Rigid cholesterol decreases fluidity and
increases melting temperature
•  Bulky cholesterol prevents phospholipids
tails from packing together making it
take lower temperatures to solidify

Fig 7-15 Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

Membranes need to be in
the fluid state to function Fig 7-15 Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Lateral diffusion can be detected using fluorescence

recovery after photobleaching (FRAP).

Fig 7-11. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

Lipids can move as much as several mm

per second within the monolayer

Fig 7-10 Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Different kinds of lipids are distributed unequally

between the two monolayers (membrane asymmetry).
Monolayers have different kinds of lipids and the
degree of saturation of fatty acids
Unaided: ~1 event per month
(although there are enzymes that
can catalyze this reaction)

Why so slow?
Would require hydrophilic heads to move all the way
through the hydrophobic interior of the bilayer

Fig 7-10 Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Membranes contain integral, peripheral

and lipid-anchored proteins.

Fig 7-19. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Freeze-fracturing allows visualization of

embedded proteins.
TECHNIQUE:

Extracellular layer

Knife

Proteins

Plasma membrane

Cytoplasmic layer
RESULTS:
SEMs show proteins as “bumps”

Fig 7-4. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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Some membrane proteins exhibit lateral

diffusion (Frye and Edidin in 1970).

Fig 6-5. Life, 10th ed. Sadava, et al.

© 2014 W.H. Freeman.

Fig 7-28. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

•  Membrane proteins vary in their mobilities

–  Some proteins can move freely, whereas others are constrained
–  Membrane proteins are more variable than lipids in their ability
to move freely within the membrane

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Radioactive labeling can distinguish

membrane protein directionality.
Membrane vesicle with proteins
•  Lactoperoxidase (LP)
attaches iodine to proteins
–  Can only cross the
membrane if in hypotonic
medium
•  Iodine can freely cross the
membrane
•  Membrane proteins are asymmetric
•  Membranes proteins do not change
orientation
•  All molecules of particular
membrane proteins are oriented the
same way
Fig 7-24. Becker’s World of the Cell, 8th ed. Hardin, et al. © 2012 Pearson.

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Membrane proteins have a variety of

functions.
1 3/4 6
1.  Enzymes
2.  Electron transport proteins
3.  Transport proteins
4.  Channel proteins
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5.  ATPases
6.  Receptors
7.  Involved in cell-cell communication
8.  Involved in stabilizing and shaping the
membrane 8
9.  Involved in cytoskeleton and extracellular
matrix attachments
Fig 7-9. Biology, 7th ed. Campbell and Reece. © 2005 Pearson.

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Questions for the weekend, #1

From what you know of the properties of membrane phospholipids, for
instance the types of structure they form spontaneously in polar solvents
such as water, what structures might they form if placed in a nonpolar, for
instance, organic solvent?

What type of structures might you expect the free fatty acid precursors of
membrane lipids to form?

If the structures formed by phospholipids and free fatty acids in nonpolar

solvents are the same, explain why? If the structures formed by
phospholipids and free fatty acids in nonpolar solvents are different,
explain why?
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Questions for the weekend, #2

For an enzyme-catalyzed reaction, the initial velocity
(v0) was determined at two different concentrations
of the substrate:
[S] (mM)
v0 (mmol/min)

1.0
2.0

4.0
2.8

Estimate the value of Km : Estimate the value of Vmax:

A.  0.17 mM A.  4.7 mmol/min
B.  5.7 mM B.  0.67 mmol/min
C.  2.7 mM C.  3.19 mmol/min
D.  0.6 mM D.  1.5 mmol/min
E.  1.7 mM E.  0.32 mmol/min
F.  Cannot be estimated from F.  Cannot be estimated from
the information provided the information provided

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