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A 1,2-diacylglycerol that has a phosphate group esterified at carbon atom 3 of the glycerol backbone is a glycerophospholipid, also known as a phosphoglyceride or a glycerol phosphatide F

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glycerols are normally soluble in benzene, chloroform, ether, and hot ethanol

Al-though triacylglycerols are insoluble in water, monoacylglycerols and diacylglycerols

readily form organized structures in water (see Chapter 9), owing to the polarity of

their free hydroxyl groups

Triacylglycerols are rich in highly reduced carbons and thus yield large amounts

of energy in the oxidative reactions of metabolism Complete oxidation of 1 g of

tri-acylglycerols yields about 38 kJ of energy, whereas proteins and carbohydrates yield

only about 17 kJ/g Also, their hydrophobic nature allows them to aggregate in

highly anhydrous forms, whereas polysaccharides and proteins are highly hydrated

For these reasons, triacylglycerols are the molecules of choice for energy storage in

animals Body fat (mainly triacylglycerols) also provides good insulation Whales

and Arctic mammals rely on body fat for both insulation and energy reserves

8.3 What Are the Structures and Chemistry

of Glycerophospholipids?

A 1,2-diacylglycerol that has a phosphate group esterified at carbon atom 3 of the

glycerol backbone is a glycerophospholipid, also known as a phosphoglyceride or a

glycerol phosphatide (Figure 8.4) These lipids form one of the largest and most

im-portant classes of natural lipids They are essential components of cell membranes

and are found in small concentrations in other parts of the cell It should be noted

A DEEPER LOOK

Polar Bears Prefer Nonpolar Food

The polar bear is magnificently adapted to thrive in its harsh

Arc-tic environment Research by Malcolm Ramsay (at the University

of Saskatchewan in Canada) and others has shown that polar

bears eat only during a few weeks out of the year and then fast

for periods of 8 months or more, consuming no food or water

during that time Eating mainly in the winter, the adult polar

bear feeds almost exclusively on seal blubber (largely composed

of triacylglycerols), thus building up its own triacylglycerol

re-serves Through the Arctic summer, the polar bear maintains

normal physical activity, roaming over long distances, but relies

entirely on its body fat for sustenance, burning as much as 1 to

1.5 kg of fat per day It neither urinates nor defecates for

ex-tended periods All the water needed to sustain life is provided

from the metabolism of triacylglycerols (because oxidation of

fatty acids yields carbon dioxide and water)

Ironically, the word Arctic comes from the ancient Greeks, who

understood that the northernmost part of the earth lay under the

stars of the constellation Ursa Major, the Great Bear Although

un-aware of the polar bear, they called this region Arktikós, which

means “the country of the great bear.”

C

O O

CH2

C

O O

CH2 O P O–

O

O–

FIGURE 8.4 Phosphatidic acid, the parent compound for glycerophospholipids.

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224 Chapter 8 Lipids

that all glycerophospholipids are members of the broader class of lipids known as

phospholipids.

The numbering and nomenclature of glycerophospholipids present a dilemma in that the number 2 carbon of the glycerol backbone of a phospholipid is asymmetric

It is possible to name these molecules either as D- or L-isomers Thus, glycerol phos-phate itself can be referred to either as D-glycerol-1-phosphate or as L -glycerol-3-phosphate (Figure 8.5) Instead of naming the glycerol phosphatides in this way,

biochemists have adopted the stereospecific numbering or sn- system The

stereospe-cific numbering system is based on the concept of prochirality If a tetrahedral

cen-ter in a molecule has two identical substituents, it is referred to as prochiral because

if either of the like substituents is converted to a different group, the tetrahedral center then becomes chiral Consider glycerol (Figure 8.5): The central carbon of glycerol is prochiral because replacing either of the CH2OH groups would make

the central carbon chiral Nomenclature for prochiral centers is based on the (R,S )

system (see Chapter 4) To name the otherwise identical substituents of a prochiral center, imagine increasing slightly the priority of one of them (by substituting a deu-terium for a hydrogen, for example) as shown in Figure 8.5 The resulting molecule

has an (S ) configuration about the (now chiral) central carbon atom The group that contains the deuterium is thus referred to as the pro-S group As a useful

exer-cise, you should confirm that labeling the other CH2OH group with a deuterium

produces the (R) configuration at the central carbon so that this latter CH2OH

group is the pro-R substituent.

Now consider the two presentations of glycerol phosphate in Figure 8.5 In the

stereospecific numbering system, the pro-S position of a prochiral atom is denoted

as the 1- position, the prochiral atom as the 2- position, and so on.When this scheme

is used, the prefix sn- precedes the molecule name (glycerol phosphate in this case)

and distinguishes this nomenclature from other approaches In this way, the

glyc-erol phosphate in natural phosphoglycerides is named sn-glycglyc-erol-3-phosphate.

Glycerophospholipids Are the Most Common Phospholipids

Phosphatidic acid, the parent compound for the glycerol-based phospholipids

(Figure 8.4), consists of sn-glycerol-3-phosphate, with fatty acids esterified at the

1- and 2-positions Phosphatidic acid is found in small amounts in most natural systems and is an important intermediate in the biosynthesis of the more common glycerophospholipids (Figure 8.6) In these compounds, a variety of polar groups are esterified to the phosphoric acid moiety of the molecule The phosphate,

HOH2C

CH2OH C

Glycerol

1CHOH D

2C

1-d, 2(S)-Glycerol (S-configuration at C-2)

CH2OH

CH2OPO3–

L -Glycerol-3-phosphate

pro-S position

pro-R position

CH2OH

CH2OPO3–

D -Glycerol-1-phosphate

sn-Glycerol-3-phosphate

(a)

(b) ACTIVE FIGURE 8.5 (a) The two

identi-cal OCH 2 OH groups on the central carbon of glycerol

may be distinguished by imagining a slight increase in

pri-ority for one of them (by replacement of an H by a D) as

shown (b) The absolute configuration of

sn-glycerol-3-phosphate is shown The pro-R and pro-S positions of the

parent glycerol are also indicated Test yourself on the

concepts in this figure at www.cengage.com/login

Go to CengageNOW at www

.cengage.com/login and click BiochemistryInteractive

to learn the structures and names of the

glycerophos-pholipids.

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together with such esterified entities, is referred to as a “head” group

Phos-phatides with choline or ethanolamine are referred to as phosphatidylcholine

(known commonly as lecithin) or phosphatidylethanolamine, respectively These

phosphatides are two of the most common constituents of biological membranes

Other common head groups found in phosphatides include glycerol, serine,

and inositol (Figure 8.6) Another kind of glycerol phosphatide found in many

tis-sues is diphosphatidylglycerol First observed in heart tissue, it is also called

cardiolipin.In cardiolipin, a phosphatidylglycerol is esterified through the C-1

hy-droxyl group of the glycerol moiety of the head group to the phosphoryl group of

another phosphatidic acid molecule

Phosphatides exist in many different varieties, depending on the fatty acids

ester-ified to the glycerol group As we shall see, the nature of the fatty acids can greatly

Phosphatidylcholine

N+ CH3

CH3

CH3

CH2CH2 O

P O–

O

CH2 C

CH2

O

H O

C O

O C O

GLYCEROLIPIDS WITH OTHER HEAD GROUPS:

NH3

CH2CH2 O

P O–

O

Phosphatidylethanolamine

CH

NH3

COO–

CH2 O P O–

O O

+

Phosphatidylserine

CH OH

CH2 O P O–

O O

Phosphatidylglycerol

CH2 OH

C

CH2 O P O–

O O

Diphosphatidylglycerol (Cardiolipin)

CH2

OH H

O P O–

O O

OH OH HO H

H H

H

H H

O P O–

O O

Phosphatidylinositol

ANIMATED FIGURE 8.6

Structures of several glycerophospholipids and space-filling models of phosphatidyl-choline, phosphatidylglycerol, and

phos-phatidylinositol See this figure animated

at www.cengage.com/login.

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226 Chapter 8 Lipids

affect the chemical and physical properties of the phosphatides and the membranes that contain them In most cases, glycerol phosphatides have a saturated fatty acid at

position 1 and an unsaturated fatty acid at position 2 of the glycerol Thus, 1-stearoyl-2-oleoyl-phosphatidylcholine(Figure 8.7) is a common constituent in natural

mem-branes, but 1-linoleoyl-2-palmitoylphosphatidylcholine is not.

Both structural and functional strategies govern the natural design of the many different kinds of glycerophospholipid head groups and fatty acids The structural roles of these different glycerophospholipid classes are described in Chapter 9 Cer-tain phospholipids, including phosphatidylinositol and phosphatidylcholine, par-ticipate in complex cellular signaling events These roles are described in Section 8.8 and Chapter 32

Ether Glycerophospholipids Include PAF and Plasmalogens

Ether glycerophospholipidspossess an ether linkage instead of an acyl group at the C-1 position of glycerol (Figure 8.8a) One of the most versatile biochemical signal

molecules found in mammals is platelet-activating factor, or PAF, a unique ether

glycerophospholipid (Figure 8.8b) The alkyl group at C-1 of PAF is typically a 16-carbon chain, but the acyl group at C-2 is a 2-carbon acetate unit By virtue of this acetate group, PAF is much more water soluble than other lipids, allowing PAF to function as a soluble messenger in signal transduction

FIGURE 8.7 A space-filling model of

1-stearoyl-2-oleoyl-phosphatidylcholine.

O

O

CH2 CH2 NH3

CH2 CH

H2C O O C

R2

Ester linkage

Ether linkage

+

(a)

O

O

CH2 CH2 N+

CH2 CH

H2C O O

CH3

CH3

CH3

CH3

Platelet-activating factor (b)

FIGURE 8.8 (a) A 1-alkyl 2-acyl-phosphatidylethanolamine (an ether glycerophospholipid) (b) The structure of

1-alkyl 2-acetyl-phosphatidylcholine, also known as platelet-activating factor or PAF.

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Plasmalogensare ether glycerophospholipids in which the alkyl moiety is cis-

,-unsaturated (Figure 8.9) Common plasmalogen head groups include choline,

ethanolamine, and serine These lipids are referred to as phosphatidal choline,

phosphatidal ethanolamine, and phosphatidal serine.

8.4 What Are Sphingolipids, and How Are They Important

for Higher Animals?

Sphingolipidsrepresent another class of lipids frequently found in biological

mem-branes An 18-carbon amino alcohol, sphingosine (Figure 8.10a), forms the

back-bone of these lipids rather than glycerol Typically, a fatty acid is joined to a

sphin-gosine via an amide linkage to form a ceramide (Figure 8.10b) Sphingomyelins

represent a phosphorus-containing subclass of sphingolipids and are especially

important in the nervous tissue of higher animals A sphingomyelin is formed

by the esterification of a phosphorylcholine or a phosphorylethanolamine to the

1-hydroxy group of a ceramide (Figure 8.10c)

There is another class of ceramide-based lipids that, like the sphingomyelins,

are important components of muscle and nerve membranes in animals These are

the glycosphingolipids, and they consist of a ceramide with one or more sugar

HUMAN BIOCHEMISTRY

Platelet-Activating Factor: A Potent Glyceroether Mediator

Platelet-activating factor (PAF) was first identified by its ability (at

low levels) to cause platelet aggregation and dilation of blood

ves-sels, but it is now known to be a potent mediator in inflammation,

allergic responses, and shock PAF effects are observed at tissue

concentrations as low as 1012M PAF causes a dramatic

inflam-mation of air passages and induces asthmalike symptoms in

labo-ratory animals Toxic shock syndrome occurs when fragments of

destroyed bacteria act as toxins and induce the synthesis of PAF

PAF causes a drop in blood pressure and a reduced volume of

blood pumped by the heart, which leads to shock and, in severe cases, death

Beneficial effects have also been attributed to PAF In repro-duction, PAF secreted by the fertilized egg is instrumental in the implantation of the egg in the uterine wall PAF is produced in significant quantities in the lungs of the fetus late in pregnancy and may stimulate the production of fetal lung surfactant, a protein–lipid complex that prevents collapse of the lungs in a newborn infant

Choline plasmalogen

N+ CH3

CH3

CH3

CH2CH2 O

P O

O –O

CH2 CH

CH2 O

O

C C H

H

The ethanolamine plasmalogens have ethanolamine in place of choline.

FIGURE 8.9 The structure and a space-filling model of a choline plasmalogen.

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228 Chapter 8 Lipids

residues in a -glycosidic linkage at the 1-hydroxyl moiety The neutral

glyco-sphingolipids contain only neutral (uncharged) sugar residues When a single

glu-cose or galactose is bound in this manner, the molecule is a cerebroside (Figure

8.10d) Another class of lipids is formed when a sulfate is esterified at the 3-position

of the galactose to make a sulfatide Gangliosides (Figure 8.10e) are more complex

glycosphingolipids that consist of a ceramide backbone with three or more sugars

esterified, one of these being a sialic acid such as N-acetylneuraminic acid These

OH

C H

H

C +NH3

OH

CH2

C

C

H

H

Sphingosine

(a)

R COOH Fatty acid

OH

C H

H

H

C

NH

OH

CH2

Ceramide

C

R O

H 2 O

C C H

O

CH2OH

H

OH

H OH

H

HO

OH C H

H

H C

NH

O

CH2

C

R O

A cerebroside

C C H

H

N+ CH3

CH 3

CH 3

CH2CH2 O

P O –O

CH 2

C O

O

OH

C H

H

C

NH

Choline sphingomyelin with stearic acid

C C H

H

O

CH2OH H OH

H OH H

HO

H H

O

CH2OH H

OH

H NH H

HO

H H O

CH3 O

O

CH2OH H

H OH

CH2OH H

H OH

H

H H O

O O

CHOH H

OH

H

H H

H N

H

CHOH

CH2OH

COO–

C

O

CH3

OH

C H

H

H

C

NH

O

CH2

C

R O

N-Acetylneuraminidate

(a sialic acid)

GM3

GM2

G M1

C C H C

FIGURE 8.10 Sphingolipids are based on the structure of sphingosine A ceramide with a phosphocholine head group is a choline sphingomyelin A ceramide with a single sugar is a cerebroside Gangliosides are cera-mides with three or more sugars esterified, one of which is a sialic acid.

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latter compounds are referred to as acidic glycosphingolipids, and they have a net

negative charge at neutral pH

The glycosphingolipids have a number of important cellular functions, despite

the fact that they are present only in small amounts in most membranes

Glyco-sphingolipids at cell surfaces appear to determine, at least in part, certain elements

of tissue and organ specificity Cell–cell recognition and tissue immunity depend on

specific glycosphingolipids Gangliosides are present in nerve endings and are

im-portant in nerve impulse transmission A number of genetically transmitted diseases

involve the accumulation of specific glycosphingolipids due to an absence of the

en-zymes needed for their degradation Such is the case for ganglioside GM2 in the

brains of Tay-Sachs disease victims, a rare but fatal childhood disease characterized

by a red spot on the retina, gradual blindness, and self-mutilation

8.5 What Are Waxes, and How Are They Used?

Waxes are esters of long-chain alcohols with long-chain fatty acids The resulting

molecule can be viewed (in analogy to the glycerolipids) as having a weakly polar

head group (the ester moiety itself) and a long, nonpolar tail (the hydrocarbon

chains) (Figure 8.11) Fatty acids found in waxes are usually saturated The alcohols

found in waxes may be saturated or unsaturated and may include sterols, such as

cholesterol (see later section) Waxes are water insoluble due to their mostly

hy-drocarbon composition As a result, this class of molecules confers water-repellant

character to animal skin, to the leaves of certain plants, and to bird feathers The

glossy surface of a polished apple results from a wax coating Carnauba wax,

ob-tained from the fronds of a species of palm tree in Brazil, is a particularly hard wax

used for high-gloss finishes, such as in automobile wax, boat wax, floor wax, and

shoe polish Lanolin,1a wool wax, is used as a base for pharmaceutical and cosmetic

products because it is rapidly assimilated by human skin The brand name Oil of

Olay®was coined by Graham Wulff, a South African chemist who developed it The

name refers to lanolin, a key ingredient

8.6 What Are Terpenes, and What Is Their Relevance

to Biological Systems?

The terpenes are a class of lipids formed from combinations of two or more

mole-cules of 2-methyl-1,3-butadiene, better known as isoprene (a five-carbon unit that is

abbreviated C5) A monoterpene (C10) consists of two isoprene units, a sesquiterpene

A DEEPER LOOK

Moby Dick and Spermaceti: A Valuable Wax from Whale Oil

When oil from the head of the sperm whale is cooled, spermaceti,

a translucent wax with a white, pearly luster, crystallizes from the

mixture Spermaceti, which makes up 11% of whale oil, is

com-posed mainly of the wax cetyl palmitate:

CH3(CH2)14OCOOO(CH2)15CH3

as well as smaller amounts of cetyl alcohol:

HOO(CH2)15CH3

Spermaceti and cetyl palmitate have been widely used in the

mak-ing of cosmetics, fragrant soaps, and candles

In the literary classic Moby Dick, Herman Melville describes

Ishmael’s impressions of spermaceti, when he muses that the waxes “discharged all their opulence, like fully ripe grapes their wine; as I snuffed that uncontaminated aroma—literally and truly, like the smell of spring violets.”*

*Melville, H., 1984 Moby Dick London: Octopus Books, p 205 (Adapted from Waddell, T G., and Sanderlin, R R., 1986 Chemistry in Moby Dick.

Journal of Chemical Education 63:1019–1020.)

1 Lanolin is a complex mixture of waxes with 33 different alcohols esterified to 36 different fatty acids.

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230 Chapter 8 Lipids

O

CH2

Stearyl palmitate

O

CH2

Triacontanol palmitate

O

R2

R1

General forumula of a wax

O

Stearic acid Oleoyl alcohol

the principal component of beeswax Waxes are components of the waxy coating on the leaves of plants, such

as jade plants (shown here) Such species typically contain dozens of different waxy esters.

C C

CH2

CH3

H2C H

Head-to-tail linkage

OH

Tail-to-tail linkage R

R

FIGURE 8.12 The structure of isoprene

(2-methyl-1,3-butadiene) and the structure of head-to-tail and

tail-to-tail linkages Isoprene itself can be formed by distillation

of natural rubber, a linear head-to-tail polymer of

iso-prene units.

O C

OH

Gibberellic acid

HO

COOH

H

H

CH3

DITERPENES

CH2OH

Phytol

O

HO

Eudesmol

CHO

HO

H

Lanosterol

TRITERPENES

Lycopene

MONOTERPENES

Limonene Citronellal Menthol

OH

CHO

Squalene

SESQUITERPENES

Bisabolene

TETRATERPENES

All-trans-retinal

ACTIVE FIGURE 8.13 Many monoterpenes are readily recognized by their characteristic flavors

or odors (limonene in lemons; citronellal in roses, geraniums, and some perfumes; and menthol from peppermint, used in cough drops and nasal inhalers) The diterpenes, which are C 20 terpenes, include retinal (the essential light-absorbing pigment in rhodopsin, the photoreceptor protein of the eye), and phytol (a constituent of chlorophyll) The triterpene lanosterol is a constituent of wool fat Lycopene is a carotenoid found in ripe fruit,

especially tomatoes Test yourself on the concepts in this figure at www.cengage.com/login

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(C15) consists of three isoprene units, a diterpene (C20) has four isoprene units, and

so on Isoprene units can be linked in terpenes to form straight-chain or cyclic

mol-ecules, and the usual method of linking isoprene units is head to tail (Figure 8.12)

Monoterpenes occur in all higher plants, whereas sesquiterpenes and diterpenes are

less widely known Several examples of these classes of terpenes are shown in Figure

8.13 The triterpenes are C30terpenes and include squalene and lanosterol, two of

the precursors of cholesterol and other steroids (discussed later) Tetraterpenes

(C40) are less common but include the carotenoids, a class of colorful photosynthetic

pigments -Carotene is the precursor of vitamin A, whereas lycopene, similar to

-carotene, is a pigment found in tomatoes.

Long-chain polyisoprenoid molecules with a terminal alcohol moiety are called

polyprenols The dolichols, one class of polyprenols (Figure 8.14), consist of 16 to

22 isoprene units and, in the form of dolichyl phosphates, function to carry

carbo-hydrate units in the biosynthesis of glycoproteins in animals Polyprenyl groups

serve to anchor certain proteins to biological membranes (discussed in Chapter 9)

The Membranes of Archaea Are Rich in Isoprene-Based Lipids Archaea are

found primarily in harsh environments Some thrive in the high temperatures of

geysers and ocean steam vents, whereas others are found in extremely acidic, cold,

or salty environments Archaea also live in extremes of pH in the digestive tracts

of cows, termites, and humans Archaea are ideally adapted to their harsh

CH3

O–

Dolichol phosphate

H3C C HC

CH3

CH2

9

CH2

Undecaprenyl alcohol (bactoprenol)

CH3

CH3

CH2OH

13 – 23

FIGURE 8.14 Dolichol phosphate is an initiation point for the synthesis of carbohydrate polymers in animals.

The analogous alcohol in bacterial systems,

undeca-prenol, also known as bactoundeca-prenol, consists of 11

iso-prene units Undecaprenyl phosphate delivers sugars from the cytoplasm for the synthesis of cell wall compo-nents such as peptidoglycans, lipopolysaccharides, and glycoproteins.

A DEEPER LOOK

Why Do Plants Emit Isoprene?

The Blue Ridge Mountains of Virginia are so named for the misty

blue vapor or haze that hangs over them through much of the

summer season This haze is composed in part of isoprene that

is produced and emitted by the plants and trees of the

moun-tains Global emission of isoprene from vegetation is estimated at

3 1014g/yr Plants frequently emit as much as 15% of the

car-bon fixed in photosynthesis as isoprene, and Thomas Sharkey, a

botanist at the University of Wisconsin, has shown that the kudzu

plant can emit as much as 67% of its fixed carbon as isoprene as

the result of water stress Why should plants and trees emit large

amounts of isoprene and other hydrocarbons? Sharkey has

shown that an isoprene atmosphere or “blanket” can protect

leaves from irreversible damage induced by high (summerlike)

temperatures He hypothesizes that isoprene in the air around

plants dissolves into leaf-cell membranes, altering the lipid

bi-layer and/or lipid–protein and protein–protein interactions

within the membrane to increase thermal tolerance 䊱 Blue Ridge Mountains

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232 Chapter 8 Lipids

environments, and one such adaptation is found in their cell membranes, which contain isoprene-based lipids (Figure 8.15) These isoprene chains are linked at both ends by ether bonds to glycerols Ether bonds are more stable to hydrolysis than the ester linkages of glycerophospholipids (Figure 8.6) With a length twice that of typical glycerophospholipids, these molecules can completely span a cell membrane, providing additional stability Interestingly, the glycerols in archaeal

lipids are in the (R ) configuration, whereas glycerolipids of animals, plants, and eu-bacteria are almost always in the (S ) configuration.

HUMAN BIOCHEMISTRY

Coumadin or Warfarin—Agent of Life or Death

The isoprene-derived molecule whose structure is shown here is

known alternately as Coumadin and warfarin By the former

name, it is a widely prescribed anticoagulant By the latter name,

it is a component of rodent poisons How can the same

chemi-cal species be used for such disparate purposes? The key to both

uses lies in its ability to act as an antagonist of vitamin K in the

body

Vitamin K is necessary for the carboxylation of glutamate

residues on certain proteins, including some proteins in the

blood-clotting cascade (including prothrombin, factor VII, factor IX, and

factor X, which undergo a Ca2-dependent conformational change

in the course of their biological activity, as well as protein C and

protein S,two regulatory proteins in coagulation) Carboxylation

of these coagulation factors is catalyzed by a carboxylase that

re-quires the reduced form of vitamin K (vitamin KH2), molecular

oxygen, and carbon dioxide KH2is oxidized to vitamin K epoxide,

which is recycled to KH2by the enzymes vitamin K epoxide

reduc-tase (1) and vitamin K reductase (2, 3) Coumadin/warfarin exerts

its anticoagulant effect by inhibiting vitamin K epoxide reductase

and possibly also vitamin K reductase This inhibition depletes

vit-amin KH2and reduces the activity of the carboxylase

Coumadin/warfarin, given at a typical dosage of 4 to 5 mg/day,

prevents the deleterious formation in the bloodstream of small

blood clots and thus reduces the risk of heart attacks and strokes for

individuals whose arteries contain sclerotic plaques Taken in much

larger doses, as for example in rodent poisons, Coumadin/warfarin

can cause massive hemorrhages and death

K

K

1 2

3

Warfarin resistant

CH HO

O

O

CH3

CH2 C

Warfarin (Coumadin)

O

H

O

-O C

CH2 Glu O

H2C

O

O

CH2

CO2

O C

O

O H

-carboxy-Glu

Warfarin inhibits

CH2OH

O

CH2 O

H2C O

H HOCH2

Isoprene units

Caldarchaeol

Glycerol Glycerol

FIGURE 8.15 The structure of caldarchaeol, an isoprene-based lipid found in archaea.

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