Lipids Lehninger

Reference: Nelson, D. L., & Cox, M. M. (2008). Principles of Biochemistry, Fifth Edition. New York: W H.
Freeman
and Company .
10.1 Storage Lipids
A. Fatty Acids Are Hydrocarbon Derivatives

1. Cis natural; trans from dairy, meat, hydrogenation of fish or vegetable oils  inc LDL
2. Longer, fewer (=), lower solubility
3. Saturated: waxy solid; Unsaturated: oily liquids
4. Melting point
i. Saturated permit rotation  flexible
ii. Cis kinks interferes with this tight packing and results in less stable aggregates takes less thermal
energy to disorder, lower M pt.
B. Triacylglycerols Are Fatty Acid Esters of Glycerol (1)
1. nonpolar, hydrophobic molecules, essentially insoluble in water
2. have lower specific gravities than water
3. Provide stored energy and insulation
4. Lipases - enzymes that catalyze the hydrolysis of stored triacylglycerols, releasing fatty acids for export to
sites where they are required as fuel
5. Advantages over carbs
i. Cs are more reduced, oxidation forms more energy
ii. hydrophobic and therefore unhydrated, the organism that carries fat as fuel does not have to carry the
extra weight of water of hydration that is associated with stored polysaccharides
6. Food
i. Veg oil unsat to sat: Catalytic hydrogenation, which reduces some of their double bonds to single
bonds and converts others to trans double bonds
ii. Rancidity result from the oxidative cleavage of the double bonds
C. Waxes Serve as Energy Stores and Water Repellents
10.2 Structural Lipids in Membranes
 Phospholipids -polar head group is joined to the hydrophobic moiety by a phosphodiester linkage
 Glycolipids - sphingolipids lack phosphate but have a simple sugar or complex oligosaccharide at their
polar ends
A. Glycerophospholipids Are Derivatives of Phosphatidic Acid
1. Becomes prochiral
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2. polar alcohol may be negatively charged (as in phosphatidylinositol 4,5-bisphosphate), neutral
(phosphatidylserine), or positively charged (phosphatidylcholine, phosphatidylethanolamine)
B. Some Phospholipids Have Ether-Linked Fatty Acids
1. As in plasmalogens in vertebrate heart tissue
2. Resistance to the phospholipases that cleave ester-linked fatty acids from membrane lipids
C. Chloroplasts Contain Galactolipids and Sulfolipids
1. Galactolipids (2)
D. Archaebacteria Contain Unique Membrane Lipid

1. ether bonds, which are much more stable to hydrolysis at low pH and high temperature than are the ester
bonds found in the lipids of eubacteria and eukaryotes
2. glycerol dialkyl glycerol tetraethers (GDGTs)
E. Sphingolipids Are Derivatives of Sphingosine (4)
1. No glycerols
2. long-chain amino alcohol sphingosine (also called 4-sphingenine
3. ceramide - When a fatty acid is attached in amide linkage to the -NH2 on C-2, structural
4. Derivatives of ceramide that differ in head groups:
i. Sphingomyelins contain phosphocholine or phosphoethanolamine //also glycerophospholipids
a. prominent in myelin, a membranous sheath that surrounds and insulates the axons of some
neurons
ii. Glycosphingolipids – neutral uncharged
a. one or more sugars connected directly to the -OH at C-1 of the ceramide moiety; they do not
contain phosphate
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b. Cerebrosides have a single sugar linked to ceramide.
c. Globosides with two or more sugars, usually Dglucose, D-galactose, or N-acetyl-D-galactosamine
iii. Gangliosides
a. oligosaccharides as their polar head groups and one or more residues of N-acetylneuraminic acid
(Neu5Ac), a sialic acid
F. Sphingolipids at Cell Surfaces Are Sites of Biological Recognition

1. carbohydrate moieties of certain sphingolipids define the human blood groups and therefore determine
the type of blood that individuals can safely receive in blood transfusions
G. Phospholipids and Sphingolipids Are Degraded in Lysosomes
1. Phospholipases of the A type remove one of the two fatty acids, producing a lysophospholipid.
2. Gangliosides are degraded by a set of lysosomal enzymes that catalyze the stepwise removal of sugar
units, finally yielding a ceramide.
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H. Sterols Have Four Fused Carbon Rings (5)
1. structural lipids present in the membranes of most eukaryotic cells
2. Cholesterol
i. amphipathic, with a polar head group (the hydroxyl group at C-3) and a nonpolar hydrocarbon body
(the steroid nucleus and the hydrocarbon side chain at C-17)
3. Steroid hormones, for example, are potent biological signals that regulate gene expression.
4. Bile acids are polar derivatives of cholesterol that act as detergents in the intestine, emulsifying dietary
fats to make them more readily accessible to digestive lipases.
 Polar – glycerophospholipids, sterols
 Chloroplast – sulfonated sugar residue so (-) charge
 Archaebacteria ethers – stable under harsh
10.3 Lipids as Signals, Cofactors, and Pigments
A. Phosphatidylinositols and Sphingosine Derivatives Act as Intracellular Signals
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B. Eicosanoids Carry Messages to Nearby Cells
-derived from arachidonic acid (20:4(Δ5,8,11,14)
-Three classes of eicosanoids: Potent hormones:
1. Prostaglandins (PG)
i. five-carbon ring
ii. PGE, for ether-soluble, and PGF, for phosphate
iii. regulating the synthesis of the intracellular messenger 3,5-cyclic AMP
iv. elevate body temperature (producing fever) and cause inflammation and pain
2. Thromboxanes
i. six-membered ring containing an ether
ii. NSAIDS inhibit the enzyme prostaglandin H2 synthase (also called cyclooxygenase or COX), which
catalyzes an early step in the pathway from arachidonate to prostaglandins and thromboxanes
iii. act in the formation of blood clots and the reduction of blood flow
3. Leukotrienes
i. three conjugated double bonds
ii. biological signals
iii. leukotriene D4, derived from leukotriene A4, induces contraction of the muscle lining the airways to
the lung  asthma, anaphylactic shock
C. Steroid Hormones Carry Messages between Tissues
1. oxidized derivatives of sterols
2. more polar than cholesterol
3. Prednisone and prednisolone are steroid drugs with potent antiinflammatory activities, mediated in part
by the inhibition of arachidonate release by phospholipase A2
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D. Plants Use Phosphatidylinositols, Steroids, and Eicosanoidlike Compounds in Signaling
E. Vitamins A and D Are Hormone Precursors
1. fat-soluble group was resolved into the four vitamin groups A, D, E, and K, all of which are isoprenoid
compounds synthesized by the condensation of multiple isoprene units.
2. Vitamin D3 / cholecalciferol
i. 7-dehydrocholesterol in a photochemical reaction driven by the UV component of sunlight
ii. converted by enzymes in the liver and kidney to 1,25-dihydroxycholecalciferol, a hormone that
regulates calcium uptake in the intestine and calcium levels in kidney and bone
3. Vitamin D2 (ergocalciferol) is a commercial product formed by UV irradiation of the ergosterol of yeast.
4. Vitamin A (retinol)
i. visual pigment of the vertebrate eye
F. Vitamins E and K and the Lipid Quinones Are Oxidation-Reduction Cofactors

1. Vitamin E / tocopherols
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i. substituted aromatic ring and a long isoprenoid side chain
ii. biological antioxidants
iii. aromatic ring reacts with and destroys the most reactive forms of oxygen radicals and other free
radicals, protecting unsaturated fatty acids from oxidation and preventing oxidative damage
2. vitamin K
i. cycle of oxidation and reduction during the formation of active prothrombin, a blood plasma protein
essential in blood clot formation
3. Warfarin is a synthetic compound that inhibits the formation of active prothrombin.
4. Ubiquinone (also called coenzyme Q) and plastoquinone are isoprenoids that function as lipophilic
electron carriers in the oxidation-reduction reactions that drive ATP synthesis in mitochondria and
chloroplasts
G. Dolichols Activate Sugar Precursors for Biosynthesis
1. isoprenoid alcohols
2. strong hydrophobic interactions with membrane lipids, anchoring the attached sugars to the membrane,
where they participate in sugar-transfer reactions
3. for use in the synthesis of certain complex carbohydrates, glycolipids, and glycoproteins
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Reference: Nelson, D. L., & Cox, M. M. (2008). Principles of Biochemistry, Fifth Edition. New York: W H.

10.1 Storage Lipids

A. Fatty Acids Are Hydrocarbon Derivatives

10.2 Structural Lipids in Membranes

D. Archaebacteria Contain Unique Membrane Lipid

F. Sphingolipids at Cell Surfaces Are Sites of Biological Recognition

10.3 Lipids as Signals, Cofactors, and Pigments

A. Phosphatidylinositols and Sphingosine Derivatives Act as Intracellular Signals

F. Vitamins E and K and the Lipid Quinones Are Oxidation-Reduction Cofactors

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