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The ␣-Ketoglutarate Family of Amino Acids Includes Glu, Gln,Pro, Arg, and Lys Amino acids derived from -ketoglutarate include glutamate Glu, glutamine Gln, proline Pro, arginine Arg, an

Trang 1

The ␣-Ketoglutarate Family of Amino Acids Includes Glu, Gln,

Pro, Arg, and Lys

Amino acids derived from -ketoglutarate include glutamate (Glu), glutamine

(Gln), proline (Pro), arginine (Arg), and in fungi and protoctists such as Euglena,

lysine (Lys) The routes for Glu and Gln synthesis were described when we

consid-ered pathways of ammonium assimilation

Proline is derived from glutamate via a series of four reactions involving

activation, then reduction, of the -carboxyl group to an aldehyde

(glutamate-5-semialdehyde), which spontaneously cyclizes to yield the internal Schiff base,

 1 - pyrroline-5-carboxylate (Figure 25.20) NADPH-dependent reduction of the

pyrro-line double bond gives propyrro-line

Arginine biosynthesis involves enzymatic steps that are also part of the urea

cycle,a metabolic pathway that allows certain animals (including humans) to

ex-crete any excess nitrogen arising from overconsumption of protein Net synthesis

of arginine depends on the formation of ornithine Interestingly, ornithine is

de-rived from glutamate via a reaction pathway reminiscent of the proline

biosyn-thetic pathway (Figure 25.21) Glutamate is first N-acetylated in an acetyl-CoA–

dependent reaction to yield N-acetylglutamate (Figure 25.21) An ATP-dependent

phosphorylation of N-acetylglutamate to give N-acetylglutamate-5- phosphate primes

this substrate for a reduced pyridine nucleotide-dependent reduction to the

semi-aldehyde N -acetyl5-semialdehyde then is aminated by a

glutamate-dependent aminotransferase, giving N-acetylornithine, which is deacylated to

orni-thine In mammals, ornithine is made from glutamate via a pathway that does not

involve an N -acetyl block.

Ornithine has three metabolic roles: (1) to serve as a precursor to arginine, (2) to

function as an intermediate in the urea cycle, and (3) to act as an intermediate in

Arg degradation In any case, the -NH3of ornithine is carbamoylated in a

reac-tion catalyzed by ornithine transcarbamoylase The carbamoyl group is derived

from carbamoyl-P synthesized by carbamoyl-phosphate synthetase I (CPS-I) CPS-I

is the mitochondrial CPS isozyme; it uses two ATPs in catalyzing the formation of

carbamoyl-P from NH3 and HCO3 , one to activate the bicarbonate ion and the

other to phosphorylate the carbamate arising from carboxyphosphate through its

1

NH3+ –O

C O

O

O

P O–

–O

CH2 CH2 C

H C O–

O

NH3+ C

O

CH2 CH2 C

H C O–

O

NAD(P)+

NAD(P)H

2

NH3+ C

O

CH2 CH2 C

H C O–

O

H

3

H2 C

H2 C C

H C

H

O–

O

NAD(P)H

H +

H +

H2O

Pi

+

+

4

NAD(P)+

H

H2

C

H2

C

C

H C

O–

O H

H

Glutamate-5-semialdehyde Proline

Δ1 -Pyrroline-5-carboxylate

FIGURE 25.20 The pathway of proline biosynthesis from glutamate.The enzymes are (1)-glutamyl kinase,

(2) glutamate-5-semialdehyde dehydrogenase, and (4)1-pyrroline-5-carboxylate reductase; reaction (3) occurs

nonenzymatically.

Trang 2

reaction with the ammonium ion (Figure 25.22) CPS-I represents the committed

step in the urea cycle, and CPS-I is allosterically activated by N-acetylglutamate Be-cause N-acetylglutamate is both a precursor to ornithine synthesis and essential to

the operation of the urea cycle, it serves to coordinate these related pathways

The product of the ornithine transcarbamoylase reaction is citrulline (Figure

25.23) Ornithine and citrulline are two -amino acids of metabolic importance that nevertheless are not among the 20 -amino acids commonly found in

pro-teins Like CPS-I, ornithine transcarbamoylase is a mitochondrial enzyme The re-actions of ornithine synthesis and the rest of the urea cycle enzymes occur in the cytosol

The pertinent feature of the citrulline side chain is the ureido group In a com-plex reaction catalyzed by argininosuccinate synthetase, this ureido group is first

ac-tivated by ATP to yield a citrullyl-AMP derivative, followed by displacement of AMP

by aspartate to give argininosuccinate (Figure 25.23) The formation of arginine is

then accomplished by argininosuccinase, which catalyzes the nonhydrolytic

elimi-nation of fumarate from argininosuccinate This reaction completes the biosynthe-sis of Arg

1

NH3+ –O

C O

O

–O

P O O–

CH2 CH2 C

H C O–

O

NH C

O

CH2 CH2 C

H C O– O

2

H

5

C O–

O

H3C C

CH3

NH C

O

CH2 CH2 C

H C O

CH3

NAD(P)+

3

NH C

O

CH2 CH2 C

H C

CH3

4

NH

H2O

CH2

H C O

CH3

CH3

CH2 CH2 C

H C

O +H3N

NH3+ +H3N

O

CH2

CH2

ATP

Glutamate

N-Acetylglutamate

N-Acetylglutamate-5-semialdehyde

SCoA

N-Acetylglutamate-5-P

Glutamate

-Ketoglutarate

CoASH

ADP

FIGURE 25.21 The bacterial pathway of ornithine biosynthesis from glutamate The enzymes are

(1) N-acetylglutamate synthase, (2) N-acetylglutamate kinase, (3) N-acetylglutamate-5-semialdehyde

dehydrogenase, (4) N-acetylornithine -aminotransferase, and (5) N-acetylornithine deacetylase.

Trang 3

The Urea Cycle Acts to Excrete Excess N Through Arg Breakdown

The carbon skeleton of arginine is derived principally from -ketoglutarate, but the

N and C atoms composing the guanidino group (Figure 25.23) of the Arg side chain

come from NH4 , HCO3 (as carbamoyl-P), and the -NH2groups of glutamate and

aspartate The circle of the urea cycle is closed when ornithine is regenerated from

Arg by the arginase-catalyzed hydrolysis of arginine Urea is the other product of

this reaction and lends its name to the cycle Note that the N atoms in urea arose

from NH4 and the Asp amino group In terrestrial vertebrates, urea synthesis is

re-quired to excrete excess nitrogen generated by increased amino acid catabolism—

for example, following dietary consumption of more than adequate amounts of

pro-tein Urea formation is basically confined to the liver

A healthy adult human male eating a typical American diet will consume about

100 g of protein per day Because such an individual will remain in nitrogen balance

(neither increasing or decreasing his net protein levels), his body must dispose of

about 1 mole of excess N derived from the amino acids in this dietary protein

Glu-tamate is key to this process because of the position of gluGlu-tamate dehydrogenase at

the interface of amino acid and carbohydrate metabolism and the importance of

glu-tamate to the urea cycle

Increases in amino acid catabolism lead to elevated glutamate levels and a rise in

N-acetylglutamate, the allosteric activator of CPS-I Stimulation of CPS-I raises

over-all urea cycle activity because activities of the remaining enzymes of the cycle simply

respond to increased substrate availability Removal of potentially toxic NH4  by

CPS-I is another important aspect of this regulation The urea cycle is linked to the

citric acid cycle through fumarate, a by-product of the action of argininosuccinase

(Figure 25.23, reaction 3)

Lysinebiosynthesis in some fungi and in the protoctist Euglena also stems from

-ketoglutarate, making lysine a member of the -ketoglutarate family of amino acids

+

δ +

1

C

O

O

O–

P

O

O O–

P

O

O O–

P

O

CH2

NH2

O

HO C

O

O–

O–

P O

2

C

O

NH2 –O

+

3

O O

O–

P

C NH2

Overall: 2 +HCO3– + NH3

O C

O–

P

O

+ 2 ADP + Pi

Pi

N

N N

ATP

ATP

Bicarbonate ion

NH3

Carbonyl-P

intermediate

Carbamate

Carbamoyl-P

ADP ADP

FIGURE 25.22 The mechanism of action of CPS-I.

Trang 4

R

1

P P

H2N C

O

NH2

NH2+

O

C

–O

NH

CH2

C NH3+ H

C

NH2

CH2

CH2

O

–O

C C C C

O

O–

NH2+

O

C

–O

N

CH2

C NH3+ H

C

N

CH2

CH2

H H

C C H

O –O

CH2 C

O

O–

NH2+

O

C

–O

N

CH2

C NH3+ H

C

CH2

CH2

H

O P

O O

–O

NH2

O

C N

CH2

C NH3+ H

C

CH2

CH2

H O

P

O O

–O

O–

C

O

H2N

2a

2b

3 4

NH3+

O

CH2

CH2

CH2

C NH3+ H

C

H H

–O

–O

A

ATP

H2O

Arginine

Fumarate

Argininosuccinate

Citrullyl-AMP

Citrulline

Carbamoyl-P

Citrulline transporter

Citrulline

Aspartate

Guanidino group Urea

Ornithine transporter

Ureido group MITOCHONDRION

Ornithine

Cytosol

AMP

ACTIVE FIGURE 25.23 The urea cycle series of reactions:The enzymes are (1) ornithine

trans-carbamoylase (OTCase), (2a and 2b) argininosuccinate synthetase, (3) argininosuccinase, and (4) arginase Test

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

Trang 5

in these organisms (As we shall see, the other organisms capable of lysine synthesis—

namely, bacteria, other fungi, algae, and green plants—use aspartate as a precursor.)

To make lysine from -ketoglutarate requires a lengthening of the carbon skeleton by

one CH2unit to yield -ketoadipate (Figure 25.24) This addition is accomplished by a

series of reactions reminiscent of the initial stages of the citric acid cycle First, a

two-carbon acetyl-CoA unit is added to the -carbon of -ketoglutarate to form

homo-citrate Then, in a reaction sequence like that catalyzed by aconitase, homoisocitrate

is formed from homocitrate Oxidative decarboxylation (as in isocitrate

dehydroge-nase) removes one carbon (the original -carboxyl group of -ketoglutarate), leaving

-ketoadipate A glutamate-dependent aminotransferase enzyme then aminates

-ketoadipate to give -aminoadipate Next, the -COOgroup is activated in an

ATP-dependent adenylylation reaction, priming this -COOgroup for reduction to an

aldehyde by NADPH -Aminoadipic-6-semialdehyde is then reductively aminated by

ad-dition of glutamate to its aldehydic carbon in an NADPH-dependent reaction leading

to the formation of saccharopine Oxidative cleavage of saccharopine by way of an

NAD-dependent dehydrogenase activity yields -ketoglutarate and lysine This

path-way is known as the ␣-aminoadipic acid pathway of lysine biosynthesis Interestingly,

ly-sine degradation in animals leads to formation of -aminoadipate by a reverse series of

reactions identical to those occurring along the last steps of this biosynthetic pathway

The Aspartate Family of Amino Acids Includes Asp, Asn, Lys,

Met, Thr, and Ile

The members of the aspartate family of amino acids include aspartate (Asp),

as-paragine (Asn), lysine (via the diaminopimelic acid pathway), methionine (Met),

threonine (Thr), and isoleucine (Ile)

Aspartateis formed from the citric acid cycle intermediate oxaloacetate by

trans-fer of an amino group from glutamate via a PLP-dependent aminotranstrans-ferase

reac-tion (Figure 25.25) Like glutamate synthesis from -ketoglutarate, aspartate

syn-thesis is a drain on the citric acid cycle As we already saw, the Asp amino group

serves as the N donor in the conversion of citrulline to arginine In Chapter 26, we

shall see that this ONH2is also the source of one of the N atoms of the purine ring

system during nucleotide biosynthesis, as well as the C-6-amino-group of the major

purine adenine In addition, the entire aspartate molecule is used in the

biosyn-thesis of pyrimidine nucleotides

Asparagineis formed by amidation of the -carboxyl group of aspartate In

bac-teria, in analogy with glutamine synthesis, the nitrogen added in this amidation

comes directly from NH4  In other organisms, asparagine synthetase catalyzes the

ATP-dependent transfer of the amido-N of glutamine to aspartate to yield

gluta-mate, AMP, PP, and asparagine (Figure 25.26)

A DEEPER LOOK

The Urea Cycle as Both an Ammonium and a Bicarbonate Disposal Mechanism

Excretion of excess NH4 in the innocuous form of urea has

tra-ditionally been viewed as the physiological role of the urea cycle

However, the urea cycle also provides a mechanism for the

excre-tion of excess HCO3 arising principally from -carboxyl groups

generated during the catabolism of -amino acids The following

equations illustrate this property:

(1) HCO3  2 NH4 ⎯⎯→ H2NCONH2 2 H2O H

(2) HCO3  H⎯⎯→ H2O CO2

Sum:

2 HCO3  2 NH4 ⎯⎯→ H2NCONH2 CO2 3 H2O

That is, 2 moles of HCO3 are eliminated in the synthesis of each

mole of urea: One is incorporated into the product, urea (reaction

1), and the second is simply protonated and dehydrated to form

CO2(reaction 2), which is easily excreted One interpretation of the

pre-ceding is that these coupled reactions allow a weak acid (NH 4  ) to protonate the conjugate base of a stronger acid (HCO 3  ) At first glance, this

pro-tonation would appear thermodynamically unfavorable, but recall that in the urea cycle, 4 equivalents of ATP are consumed per equiv-alent of urea synthesized: 2 ATPs in the synthesis of carbamoyl-P, and 2 more as 1 ATP is converted to AMP  PPiin the synthesis of argininosuccinate from citrulline (Figure 25.23) If this

interpreta-tion is correct, the urea cycle may be considered an ATP-driven proton

pump that transfers H  ions from NH 4  to HCO 3  against a thermody-namic barrier In the process, the potentially toxic waste products, ammo-nium and bicarbonate, are rendered innocuous and excreted.

Trang 6

H3C

NH3+

P P

C

CH2

CH2

C O

C

C O

C

CH2

CH2 C HO

C O –O

C O–

O

2

C

CH2

CH2

CH C O –O

C O–

O

C

CH2

CH2

C O –O

C O–

O C C

C

CH2

CH2

C O –O

CH2

C

CH2

CH2

C C O –O

CH2 H

4

5 6

NH3+

C

CH2

CH2

C C O –O

CH2 H

O P O O

–O

7

NH3+

H

C

CH2

CH2

C

C

O –O

CH2

H

O

8

NH3+

C

CH2

CH2

C

C

O –O

CH2

H

C O –O

CH2

CH2

C O –O

H

9

NH3+

CH2

CH2

C C O –O

CH2 H

NH3+

CH2

H

Adenosine

CH2

O

ATP

+ + H2O

H2O

H2O

H+

H+

H+

H +

CO 2

-Ketoglutarate

SCoA

+

Homocitrate cis-Homoaconitate Homoisocitrate

+ +

-Ketoadipate

Glu

-KG

-Aminoadipate

Mg 2+

6-Adenylyl--aminoadipate

Mg2+

+

-Aminoadipic-6-semialdehyde

+ +

+ Glutamate

Saccharopine

L -Lysine

NADH

NADPH

NADH

NADP+

NAD+

NADP+

NAD+

CoASH

-KG

FIGURE 25.24 Lysine biosynthesis in certain fungi and Euglena: the

-aminoadipic acid pathway.

Trang 7

–O O

C

CH2

C

+

C

CH2 C C

NH3+ H

C

CH2 C C

NH3+ H

CH2

+

C

CH2 C C

CH2

O

Oxaloacetate Glutamate Aspartate -Ketoglutarate

FIGURE 25.25 Aspartate biosynthesis via transamination

of oxaloacetate by glutamate.

HUMAN BIOCHEMISTRY

Asparagine and Leukemia

Leukemia is a cancer of the bone marrow that affects the

production of normal lymphocytes (white blood cells) Acute

lymphoblastic leukemia (ALL) and acute myeloblastic leukemia

(AML) are caused by overproduction of immature lymphocytes.

Both normal and malignant lymphocytes are highly dependent

on the uptake of asparagine from the blood for growth

Admin-istration of E coli asparaginase, an enzyme that converts Asn to

Asp and NH4 (page 806), is one chemotherapeutical approach

to treat childhood ALL and some forms of AML, but patients

of-ten develop resistance to treatment with this “foreign” protein

Inhibition of asparagine synthetase presents an alternative way

to deprive malignant lymphocytes of essential Asn, and

as-paragine synthetase inhibitors might offer a clinical strategy for

treating asparaginase-resistant leukemias The adenylated

sul-foximine shown in the figure is an analog of the aspartyl-AMP

intermediate formed in the asparagine synthetase reaction

(Fig-ure 25.26) In vitro, this compound inhibits asparagine

syn-thetase at nanomolar concentrations The polarity of this

sub-stance limits its ability to cross cell membranes and thus its use

in chemotherapy Hopefully, “second-generation” compounds based on this structure’s affinity for asparagine synthetase will lead to the development of useful drugs to treat these leukemias

OH

NH2

N N

N N O

HO

An adenylated sulfoximine

O

O P

O H

H3N +

O–

CH3

N S –O2C

P P

C

C

C

NH3+

H

CH2

+

O C

C C

NH3+ H

CH2

O C

C C

NH3+ H

CH2

NH2

ATP

AMP

O C

C C

NH3+ H

CH2

NH2

CH2

O C

C C

NH3+ H

CH2

CH2 O–

Step A

[Enz-bound intermediate]

Step B

Asparagine

+

Glutamine

+

Glutamate

AMP

H2O

FIGURE 25.26 Asparagine biosynthesis from Asp, Gln, and ATP by

asparagine synthetase.-Aspartyladenylate is an enzyme-bound

intermediate.

Trang 8

Threonine, methionine, and lysine biosynthesis in bacteria proceeds from the

common precursor aspartate, which is converted first to aspartyl- -phosphate and

then to -aspartyl-semialdehyde The first reaction is an ATP-dependent

phosphoryla-tion catalyzed by aspartokinase (Figure 25.27, reacphosphoryla-tion 1) In E coli, there are three

isozymes of aspartokinase, designated aspartokinases I, II, and III Each of these

isozymes is uniquely controlled by one of the three end-product amino acids Form

I is inhibited by threonine and form III, by lysine Form II is not feedback-inhibited, but its synthesis is repressed by methionine

-Aspartyl-semialdehyde is formed via NADPH-dependent reduction of

aspartyl--phosphate in a reaction catalyzed by ␤-aspartyl-semialdehyde dehydrogenase

(Figure 25.27, reaction 2) From here, the pathway of lysine synthesis diverges The methyl carbon of pyruvate is condensed with -aspartyl-semialdehyde, and H2O is

eliminated to yield the cyclic compound 2,3-dihydropicolinate (Figure 25.27, reaction

10) Thus, lysine synthesized by this pathway must be considered a member of both the aspartate and the pyruvate families of amino acids Lysine is a feedback

in-hibitor of this branch-point enzyme Dihydropicolinate is then reduced in an

NADPH-dependent reaction to  1 - piperidine-2,6-dicarboxylate (Figure 25.27, reaction 11) A

series of reactions, including a hydrolytic opening of the piperidine ring, a succiny-lation, a glutamate-dependent amination, and the hydrolytic removal of succinate, results in the formation of the symmetric L , L

-reactions 12 through 14) Epimerization of this intermediate to the meso form, followed by decarboxylation, yields the end product lysine (Figure 25.27,

reac-tions 15 and 16) Because this pathway proceeds through the symmetric L , L -diaminopimelate, one-half of the CO2 evolved in the terminal decarboxylase step

is derived from the carboxyl group of pyruvate and one-half from the -carboxyl

of Asp

The other metabolic branch diverging from -aspartyl-semialdehyde leads to threonine and methionine via homoserine, an analog of serine that is formed by the

NADPH-dependent reduction of -aspartyl-semialdehyde (Figure 25.27, reaction

3) catalyzed by homoserine dehydrogenase From homoserine, the biosynthetic pathways leading to methionine and threonine separate To form methionine, the OOH group of homoserine is first succinylated by homoserine acyltransferase

(Figure 25.27, reaction 6) Methionine is a feedback inhibitor of this enzyme The

succinyl group of O-succinylhomoserine is then displaced by cysteine to yield cys-tathionine (Figure 25.27, reaction 7) The sulfur atom in methionine is contributed

by a cysteine sulfhydryl Cystathionine is then split to give pyruvate, NH4 , and ho-mocysteine, a nonprotein amino acid whose side chain is one OCH2O group longer than that of Cys (Figure 25.27, reaction 8) Methylation of the homocysteine OSH

via methyl transfer from the methyl donor, N5-methyl-THF (see Chapter 26) gives methionine (Figure 25.27, reaction 9)

In passing, it is important to note the role of methionine itself in methylation

re-actions The enzyme S-adenosylmethionine synthase catalyzes the reaction of

methio-nine with ATP to form S-adenosylmethiomethio-nine, or SAM (Figure 25.28) SAM is a substrate

of methyltransferases in a variety of methyl-donor reactions, such as the formation

of phosphatidylcholine from phosphatidylethanolamine (see Figure 8.6) Following decarboxylation, SAM is a source of propylamine for the synthesis of polyamines (Figure 25.28)

The remaining amino acids of the aspartate family are threonine and isoleucine

Threonine,like methionine, is synthesized from homoserine Indeed, homoserine

is the primary alcohol analog of the secondary alcohol Thr To move this OOH from C-4 to C-3 requires activation of the hydroxyl through ATP-dependent

phos-phorylation by homoserine kinase (see Figure 25.27, reaction 4) As the first

reac-tion unique to Thr biosynthesis, homoserine kinase is feedback inhibited by

threo-nine The last step is catalyzed by threonine synthase, a PLP-dependent enzyme (see

Figure 25.27, reaction 5)

Isoleucine is included in the aspartate family of amino acids because four of its six carbons derive from Asp (via threonine) and only two come from pyruvate

Trang 9

+ +

1

HC HC

HC

HC HC

HC

HC HC

C

C O

NH3+

CH2

2

C

C

NH3+

CH2

3

C

NH3+

CH2

CH2

O H

4

–O

O

H2O

H2O

H2O

H2O

CO2

Pi

Pi

Pi

H +

H +

H +

H +

C CH2 CH2

5

–O

O

C HC

H C

H C O H

NH3

CH3

6

Succinyl-10

Pyruvate

C

NH3+

CH2

CH2

O Succ

7

Succinate Cysteine

C

NH3+

CH2

CH2 S

CH2

NH3+ C H O

8

C

NH3+

CH2

CH2 HS

9

C

NH3+

CH2

CH2 S

CH3

C

–O

NH3+

CH2

C H OH

CH2

O

10

2

O–

C

O C

O

–O

N

11

O–

C

O C

O

–O

N

Succinyl- +

12

O–

C

O C

O

O

Succ

13

O–

C

O C

O

Succ

H

NH2

C

NH3+

CH2

CH2

CH2

CH2

NH3+

16

C

NH3+

CH2

CH2

CH2

C

C NH3+ H

15

C

NH3+

CH2

CH2

CH2

C C

NH3+ H

14

O

C

C –O

+

+

C

C

CH2

NH3+

ATP

ADP

ADP

NADP+

NADPH

NADPH

CoASH

CoA

CoASH CoA

NADPH

P

O

Aspartate

Aspartyl--phosphate

Phosphohomoserine Threonine

O-Succinylhomoserine

Cystathionine

NH3 + Pyruvate

N5 -Methyl- THF

Homocysteine

THF

Methionine

2,3-Dihydropicolinate

Δ1

-Piperidine-2,6-dicarboxylate

N-Succinyl-2-amino-6-keto-L -pimelate

-Ketoglutarate

Glutamate

N-SuccinylL - L

-Lysine

mesoL - L

-L - L

-Succinate

FIGURE 25.27 Biosynthesis of threonine, methionine, and lysine, members of the aspartate family of amino acids.

Trang 10

CH3

NH3+

P P

O

S

CH2

CH2

C C

–O H

+

NH2

N

N N N

O

CH2

NH2

N

N N N

O

CH2

NH2

N

N N N

O

CH2

S+

CH3

CH2

CH2

C NH3+ H

C O –O

Mg2+

S +

CH3

CH2

CH2

NH3+

CH2

CH2 CH2 C C

NH3+

S

H3C

S

CH2

CH2

C NH3+ H

H

C O –O

Adenosine+

NH2

N

N N N

O

CH2

O

O–

HS

CH2CH2CH2CH2

CH2CH2CH2CH2 CH2CH2CH2

+ H2O

H2O

CO2

Methionine

S-Adenosylmethionine (SAM)

S-Adenosylmethionine

decarboxylase

“Decarboxylated SAM”

Methylated products Methyl acceptors

Methyl transferases

Putrescine

Spermidine

Propylamine

transferases

as in putrescine

spermidine

5 ⴕ-Methylthioadenosine

S-Adenosyl

homocysteine ATP

L -Homocysteine

FIGURE 25.28 The synthesis of S-adenosylmethionine (SAM).

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