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  • Fatty

    Aci

    d Sy

    nthe

    sis

  • Co

    mpa

    riso

    n o

    f fa

    tty

    aci

    d bi

    osy

    nth

    esis

    an

    d de

    gra

    datio

    n

  • Site

    s o

    f reg

    ula

    tion

    o

    f fa

    tty

    aci

    d m

    eta

    bolis

    m

  • The

    form

    atio

    n o

    f ma

    lon

    yl~

    Co

    A is

    the

    com

    mitt

    ed st

    ep in

    fa

    tty

    aci

    d sy

    nth

    esis

    Irrev

    ersib

    le re

    actio

    n ca

    taly

    zed

    by ac

    etyl

    Co

    A ca

    rbo

    xyl

    ase

    (ACC

    ):

    acet

    yl~

    CoA

    +

    AT

    P +

    H

    CO3-

    mal

    on

    yl~

    CoA

    + A

    DP

    + Pi

    +

    H

    +

    ACC

    co

    nta

    ins

    a bi

    otin

    pr

    ost

    hetic

    gr

    ou

    p, an

    d th

    e re

    actio

    n m

    echa

    nism

    is

    simila

    r to

    pyru

    vat

    e ca

    rbo

    xyl

    ase

    and

    pro

    pio

    nyl

    ~Co

    A ca

    rbo

    xyl

    ase

    reac

    tion

    s.

    The

    two

    st

    eps

    in th

    e re

    actio

    n:

    Bio

    tin----En

    zym

    e +

    AT

    P +

    H

    CO3-

    CO

    2-B

    iotin

    ----En

    zym

    e +

    A

    DP

    + Pi

    CO2-

    Bio

    tin----En

    zym

    e +

    ac

    etyl

    ~Co

    A m

    alo

    nyl

    ~Co

    A +

    B

    iotin

    ----En

    zym

    e

    No

    tes:

    In

    E.

    co

    li, 3

    subu

    nits

    : bi

    otin

    ca

    rbo

    xyl

    ase,

    tr

    ansc

    arbo

    xyl

    ase,

    bi

    otin

    -ca

    rbo

    xyl

    ca

    rrie

    r pr

    ote

    in.

    In bi

    rds

    and

    mam

    mal

    s a

    singl

    e po

    lype

    ptid

    e ch

    ain

    ha

    s al

    l thr

    ee fu

    nct

    ion

    s.

    ACC

    is

    subje

    ct to

    ho

    rmo

    nal

    re

    gula

    tion

    . D

    epho

    spho

    ryla

    ted

    form

    is

    activ

    e, ph

    osp

    hory

    late

    d fo

    rm is

    less

    ac

    tive.

    G

    luca

    gon

    an

    d ep

    inep

    hrin

    e st

    imu

    late

    ph

    osp

    hory

    latio

    n, In

    sulin

    st

    imu

    late

    s de

    pho

    spho

    ryla

    tion

    .

    Citr

    ate

    activ

    ates

    an

    d pa

    lmito

    yl~

    CoA

    inhi

    bits

    th

    e en

    zym

    e

    Pho

    spho

    ryla

    tion

    le

    ads

    to de

    poly

    mer

    izat

    ion

    .

  • ATP-

    depe

    nde

    nt c

    arb

    oxy

    latio

    n pr

    ovi

    des

    en

    erg

    y in

    put.

    The

    CO2

    is lo

    st la

    ter

    durin

    g co

    nde

    nsa

    tion

    w

    ith th

    e

    gro

    win

    g fa

    tty a

    cid.

    The

    sp

    on

    tan

    eo

    us

    deca

    rbo

    xyla

    tion

    dr

    ive

    s th

    e

    con

    den

    satio

    n re

    act

    ion

    .

    H 3C

    CSC

    oA

    O CH2

    CSC

    oA

    O

    OO

    Cace

    tyl-C

    oA

    mal

    onyl

    -Co

    A

    The

    in

    put t

    o fa

    tty a

    cid

    syn

    the

    sis

    is ac

    etyl

    -

    CoA

    , w

    hich

    is

    carb

    oxy

    late

    d to

    mal

    on

    yl-Co

    A.

  • As w

    ith oth

    er

    carb

    oxy

    latio

    n re

    act

    ions,

    th

    e enzy

    me pr

    ost

    hetic

    gr

    oup

    is b

    iotin

    .

    ATP-

    depe

    nde

    nt c

    arb

    oxy

    latio

    n of t

    he bi

    otin

    , ca

    rrie

    d out a

    t one act

    ive si

    te 1

    , is

    follo

    wed

    by tr

    ansf

    er

    of t

    he ca

    rboxy

    l gr

    oup

    to ace

    tyl-C

    oA

    at a

    se

    cond

    act

    ive si

    te 2

    .

    Ace

    tyl-C

    oA

    Carb

    oxyl

    ase

    cata

    lyzes

    the

    2-st

    epre

    act

    ion

    by w

    hich

    ace

    tyl-

    CoA

    is

    carb

    oxy

    late

    d to

    form

    m

    alo

    nyl

    -

    CoA

    .

    ll

    En

    zym

    e-bi

    otin

    HCO

    3- +

    AT

    P

    ADP

    + P i

    En

    zym

    e-bi

    otin

    -CO

    2-

    O

    CH

    3-C-

    SCo

    A a

    cety

    l-Co

    A O

    -

    O2C

    -CH

    2-C-

    SCo

    A m

    alo

    nyl-

    CoA

    llEn

    zym

    e-bi

    otin

    1 2

  • The

    o

    vera

    ll re

    act

    ion

    , w

    hich

    is

    sp

    on

    tan

    eou

    s, m

    ay

    be

    sum

    ma

    rize

    d a

    s:

    HCO

    3+

    ATP

    + ac

    etyl

    -Co

    A

    AD

    P+

    P i

    + m

    alo

    nyl

    -

    CoA

    ll

    En

    zym

    e-bi

    otin

    HCO

    3- +

    AT

    P

    ADP

    + P i

    En

    zym

    e-bi

    otin

    -CO

    2-

    O

    CH

    3-C-

    SCo

    A a

    cety

    l-Co

    A O

    -

    O2C

    -CH

    2-C-

    SCo

    A m

    alo

    nyl-

    CoA

    llEn

    zym

    e-bi

    otin

    1 2

  • Bio

    tin is

    linke

    d to

    th

    e enzy

    me by

    an am

    ide bo

    nd

    betw

    een

    the te

    rmin

    al c

    arb

    oxy

    l of t

    he bi

    otin

    si

    de ch

    ain

    and

    the -

    am

    ino gr

    oup

    of a

    ly

    sin

    ere

    sidu

    e.

    The co

    mbi

    ned

    biotin

    and

    lysin

    e si

    de ch

    ain

    s act

    as

    a lo

    ng

    flexib

    le ar

    mth

    at a

    llow

    s th

    e bi

    otin

    rin

    g to

    tra

    nsl

    oca

    te

    betw

    een th

    e 2

    act

    ive si

    tes.

    CHCH

    H 2C

    SCHN

    HC

    N

    O

    (CH

    2) 4C

    NH(C

    H2) 4

    CHCO

    NH

    O

    COO

    Carb

    ox

    ybio

    tin

    lysin

    e re

    sidu

    e

  • Ace

    tyl-C

    oA

    Ca

    rbo

    xyl

    ase,

    w

    hich

    co

    nve

    rts a

    cety

    l-CoA

    to

    malo

    nyl-

    CoA,

    is

    the co

    mm

    itted

    st

    epof t

    he fa

    tty a

    cid

    synt

    hesi

    s pa

    thw

    ay.

    The m

    am

    malia

    n enzy

    me is

    reg

    ula

    ted,

    by

    phosp

    hory

    latio

    n

    allo

    steric

    contro

    l by

    loca

    l meta

    bolit

    es.

    Con

    form

    atio

    nal

    ch

    ange

    sass

    oci

    ate

    d w

    ith re

    gula

    tion:

    In

    th

    e ac

    tive

    confo

    rmatio

    n, Ac

    ety

    l-CoA

    Carb

    oxy

    lase

    ass

    oci

    ate

    s to

    fo

    rm m

    ulti

    meric

    fila

    men

    tou

    sco

    mpl

    exe

    s.

    Tr

    ansi

    tion to

    th

    e in

    activ

    eco

    nfo

    rmatio

    n is

    ass

    oci

    ate

    d w

    ith

    diss

    oci

    atio

    n to

    yie

    ld th

    em

    on

    om

    eric

    form

    o

    f the

    en

    zym

    e (pr

    oto

    me

    r).

  • The de

    crea

    sed

    produ

    ctio

    n of m

    alo

    nyl

    -Co

    Apr

    eve

    nts

    energ

    y-util

    izin

    g fa

    tty a

    cid

    synt

    hesi

    s w

    hen ce

    llula

    r energ

    y st

    ore

    s are

    depl

    ete

    d. (A

    MP

    is a

    bunda

    nt o

    nly

    whe

    n AT

    P ha

    s be

    en

    ext

    ensi

    vely

    deph

    osp

    hory

    late

    d.)

    AM

    P-A

    ctiv

    ate

    d K

    ina

    seca

    taly

    zes

    pho

    spho

    ryla

    tion

    of A

    cety

    l-Co

    A Ca

    rbo

    xyl

    ase,

    cau

    sing

    inhi

    bitio

    n.

    Ph

    osp

    hory

    late

    d pr

    oto

    mer

    of

    A

    cety

    l-CoA

    Ca

    rbo

    xyl

    ase

    (inac

    tive)

    D

    epho

    spho

    ryla

    ted

    Poly

    mer

    o

    f A

    cety

    l-CoA

    Ca

    rbox

    ylas

    e (ac

    tive)

    Citr

    ate

    Dep

    hosp

    hory

    late

    d,

    e.g.

    , by

    in

    sulin

    -

    activ

    ated

    Pr

    ote

    in

    Pho

    spha

    tase

    Palm

    itoyl

    -Co

    A

    Pho

    spho

    ryla

    ted,

    e.

    g., via

    AM

    P-ac

    tivat

    ed K

    inas

    e w

    hen ce

    llula

    r st

    ress

    o

    r

    exer

    cise

    de

    plet

    es A

    TP.

    Reg

    ula

    tion

    of A

    cety

    l-CoA

    C

    arb

    oxyl

    ase

  • Whe

    n AM

    P is

    hig

    h (A

    TP lo

    w), m

    alo

    nyl-

    CoA

    produ

    ctio

    n is

    di

    min

    ishe

    d, re

    leasi

    ng

    fatty

    aci

    d oxid

    atio

    n fro

    m in

    hibi

    tion. Th

    is

    will

    lead

    to in

    crea

    sed

    ATP

    pr

    odu

    ctio

    n.

    AM

    P-A

    ctiv

    ated

    K

    inas

    eha

    s a si

    gnific

    ant r

    ole

    eve

    n in

    tissu

    es

    (e.g.

    , ca

    rdia

    c m

    usc

    le) th

    at d

    o not

    sign

    ificantly

    syn

    thesi

    ze fa

    tty

    aci

    ds.

    In su

    ch tis

    sues

    mal

    on

    yl-

    CoA

    , pr

    odu

    ced

    via one

    isofo

    rm of A

    cety

    l-CoA

    Carb

    oxy

    lase

    , fu

    nct

    ions

    main

    ly as

    an

    inhi

    bito

    rof

    fatty

    ac

    id o

    xid

    atio

    n.

    H3C

    CSC

    oA

    O CH2

    CSC

    oA

    O

    OO

    C

    acet

    yl-Co

    A

    mal

    onyl

    -Co

    A

    ATP

    +

    H

    CO3

    A

    DP

    + P i

    Ace

    tyl-C

    oA

    Carb

    oxyl

    ase

    (inhi

    bite

    d by

    AM

    P-A

    ctiv

    ated

    Kin

    ase)

  • A cA

    MP

    casc

    ade

    , a

    ctiv

    ate

    d by

    gl

    uca

    gon

    &

    epi

    ne

    phrin

    e w

    hen

    bl

    oo

    d gl

    uco

    se is

    lo

    w, m

    ay

    als

    o

    resu

    lt in

    ph

    osp

    hory

    latio

    n o

    f Ace

    tyl-C

    oA

    Carb

    oxy

    lase

    via

    cAM

    P-D

    epen

    den

    t Pro

    tein

    K

    inas

    e.

    With

    Ac

    ety

    l-Co

    A Ca

    rbo

    xyla

    se in

    hibi

    ted,

    a

    cety

    l-Co

    A re

    ma

    ins

    ava

    ilabl

    e fo

    r sy

    nth

    esi

    s o

    f ke

    ton

    e bo

    die

    s, th

    e

    alte

    rna

    tive

    m

    eta

    bolic

    fu

    el u

    sed

    whe

    n bl

    oo

    d gl

    uco

    se

    is lo

    w.

    H3C

    CSC

    oA

    O CH2

    CSC

    oA

    O

    OO

    Cace

    tyl-C

    oA

    mal

    onyl

    -Co

    A

  • The

    a

    nta

    gon

    istic

    e

    ffect

    o

    f in

    sulin

    , pr

    odu

    ced

    whe

    n

    blo

    od

    glu

    cose

    is

    hi

    gh, is

    a

    ttrib

    ute

    d to

    a

    ctiv

    atio

    n o

    f Pr

    ote

    in Ph

    osp

    hata

    se.

    Ph

    osp

    hory

    late

    d pr

    oto

    mer

    of

    A

    cety

    l-Co

    A Ca

    rbo

    xyl

    ase

    (inac

    tive)

    D

    epho

    spho

    ryla

    ted

    Poly

    mer

    o

    f A

    cety

    l-Co

    A Ca

    rbox

    ylas

    e ( ac

    tive)

    Citr

    ate

    Dep

    hosp

    hory

    late

    d,

    e.g.

    , by

    in

    sulin

    -

    activ

    ated

    Pr

    ote

    in

    Pho

    spha

    tase

    Palm

    itoyl

    -Co

    A

    Pho

    spho

    ryla

    ted,

    e.

    g., via

    AM

    P-ac

    tivat

    ed K

    inas

    e w

    hen ce

    llula

    r st

    ress

    o

    r

    exer

    cise

    de

    plet

    es A

    TP.

    Reg

    ula

    tion

    of

    A

    cety

    l-Co

    A C

    arb

    oxyl

    ase

  • Palm

    itoyl

    -Co

    A(pr

    odu

    ct of F

    atty

    Aci

    d Sy

    ntha

    se) p

    rom

    ote

    s th

    e

    inac

    tive

    confo

    rmatio

    n, di

    min

    ishi

    ng

    produ

    ctio

    n of m

    alo

    nyl-

    CoA,

    the pr

    ecu

    rsor

    of f

    atty

    aci

    d sy

    nthe

    sis.

    This

    is a

    n exa

    mpl

    e of f

    eedb

    ack

    inhi

    bitio

    n.

    Reg

    ula

    tion

    of

    Ace

    tyl-C

    oA

    Carb

    ox

    ylas

    e by

    loca

    l met

    abo

    lites

    :

    Ph

    osp

    hory

    late

    d pr

    oto

    mer

    of

    A

    cety

    l-CoA

    Ca

    rbo

    xyl

    ase

    (inac

    tive)

    D

    epho

    spho

    ryla

    ted

    Poly

    mer

    of

    A

    cety

    l-CoA

    Ca

    rboxyl

    ase

    (activ

    e)

    Citr

    ate

    Dep

    hosp

    hory

    late

    d,

    e.g.

    , by

    in

    sulin

    -

    activ

    ated

    Pr

    ote

    in

    Pho

    spha

    tase

    Palm

    itoyl

    -Co

    A

    Pho

    spho

    ryla

    ted,

    e.

    g., via

    AM

    P-ac

    tivat

    ed K

    inas

    e w

    hen ce

    llula

    r st

    ress

    o

    r

    exer

    cise

    de

    plet

    es A

    TP.

    Reg

    ula

    tion

    of A

    cety

    l-Co

    A C

    arb

    oxyl

    ase

  • [Citr

    ate

    ] is hi

    gh w

    hen

    th

    ere

    is

    a

    dequ

    ate

    a

    cety

    l-Co

    A e

    nte

    ring

    Kre

    bs Cy

    cle

    .

    Exce

    ss a

    cety

    l-Co

    A is

    th

    en

    co

    nve

    rted

    via

    m

    alo

    nyl-

    CoA

    to fa

    tty a

    cids

    fo

    r st

    ora

    ge.

    G

    luco

    se-6-

    phosp

    hata

    se

    gl

    uco

    se-6-

    P gl

    uco

    se

    G

    luco

    neo

    genes

    is G

    lyco

    lysis

    py

    ruvat

    e fa

    tty ac

    ids

    ac

    etyl

    Co

    A ke

    tone

    bodi

    es

    ch

    ole

    ster

    ol

    ox

    aloac

    etat

    e ci

    trat

    e

    K

    rebs

    Cy

    cle

    Citr

    ate

    allo

    steric

    ally

    ac

    tivat

    esAc

    ety

    l-Co

    A Ca

    rboxy

    lase

    .

  • Act

    ive,

    po

    lym

    eriz

    ed

    AC

    C

    ina

    ctiv

    e, de

    poly

    mer

    ized

    AC

    Cci

    tra

    teph

    osp

    hory

    l gro

    up

    AM

    PK

    pro

    tein

    ph

    osp

    hata

    se 2A

    oth

    er in

    sulin

    -de

    pen

    den

    t ph

    osp

    hata

    se?

    part

    ially

    po

    lym

    eriz

    ed,

    part

    ially

    a

    ctiv

    e

    palm

    itoyl

    ~C

    oA

    palm

    itoyl

    ~C

    oA

    An

    hy

    poth

    esis

    for

    the

    regu

    latio

    n o

    f AC

    C

    Ener

    gy ch

    arge

    o

    f cel

    l co

    ntr

    ols

    AM

    PK.

    Epin

    ephr

    ine

    and

    glu

    cago

    n ac

    t by

    cau

    sing

    inhi

    bitio

    n o

    f PP2

    AIn

    sulin

    ac

    ts th

    rou

    gh u

    nkn

    ow

    n ph

    osp

    hata

    se

    palm

    itoyl

    ~Co

    A di

    sper

    ses

    filam

    ents

    pho

    spho

    ryla

    tion

    in

    hibi

    ts fo

    rmat

    ion

    o

    f fila

    men

    tsci

    trat

    e pr

    om

    ote

    s po

    lym

    eriz

    atio

    n

  • Fatty

    ac

    id sy

    nth

    esi

    sfro

    m a

    cety

    l-Co

    A &

    ma

    lon

    yl-Co

    A o

    ccu

    rs by

    a

    se

    ries

    of r

    ea

    ctio

    ns

    tha

    t are

    :

    in

    ba

    cter

    iaca

    talyz

    ed

    by se

    ven

    se

    para

    te

    en

    zym

    es.

    in

    m

    amm

    als

    cata

    lyze

    d by

    in

    divi

    dua

    l do

    ma

    ins

    of

    a si

    ngl

    e la

    rge

    po

    lype

    ptid

    e.

    Evo

    lutio

    n o

    f the

    m

    am

    ma

    lian

    Fa

    tty A

    cid

    Syn

    thas

    ea

    ppa

    ren

    tly ha

    s in

    volv

    ed

    gen

    e fu

    sio

    n.

    NA

    DPH

    serv

    es

    as

    elec

    tro

    n do

    no

    rin

    tw

    o re

    act

    ion

    s in

    volv

    ing

    subs

    trate

    re

    duct

    ion

    .

    The

    N

    ADPH

    is

    pr

    odu

    ced

    ma

    inly

    by th

    e Pe

    nto

    se

    Pho

    spha

    te Pa

    thw

    ay.

  • Ma

    mm

    alia

    n Fa

    tty

    Aci

    d Sy

    nth

    ase

    (F

    AS)

    keto

    acyl

    -A

    CP sy

    nth

    ase

    mal

    on

    yl/a

    cety

    l-Co

    AA

    CP tr

    ansa

    cyla

    se

    hydr

    ox

    yacy

    l-ACP

    de

    hydr

    atas

    e

    eno

    yl-A

    CP re

    duct

    ase

    keto

    acyl

    -A

    CP re

    duct

    ase

    palm

    itoyl

    th

    ioes

    tera

    se

    Ma

    mm

    alia

    n en

    zym

    e is

    a ho

    mo

    dim

    er o

    f 272

    kD

    a su

    bun

    its

    Mem

    ber

    of t

    he m

    ega

    syn

    tha

    se fa

    mily

    .

    In E.

    co

    li 7

    diffe

    ren

    t en

    zym

    es +

    A

    CP

  • Fatty

    Aci

    dSy

    ntha

    se

    prost

    hetic

    gro

    ups

    :

    th

    e th

    iolo

    f the

    si

    de-

    chain

    of a

    cy

    stei

    ne

    resi

    due of C

    onde

    nsi

    ng

    Enzy

    me do

    main

    .

    th

    e th

    iolo

    f ph

    osp

    hopa

    nte

    thei

    ne,

    equ

    ivale

    nt i

    n st

    ruct

    ure

    to

    part

    of c

    oenzy

    me A.

    N

    NNN

    NH 2 O

    OH

    O

    HH

    H

    CH2

    H

    OP

    OP

    OH 2

    C

    O

    OO O

    P O

    O

    O

    CCCNHCH2

    CH2

    CNH

    CH3

    H 3C

    HH

    O

    O

    CH2

    CH2

    SH

    O-m

    erca

    ptoet

    hyla

    min

    e

    panto

    then

    ate

    AD

    P-3'-

    phosp

    hate

    Coen

    zym

    e A

    phosp

    hopa

    nte

    thei

    ne

    H3N

    +C

    COO

    CH2

    SHH

    cyst

    eine

  • The

    pho

    spho

    pan

    teth

    ein

    e pr

    ost

    hetic

    gr

    ou

    p o

    f AC

    P is

    deri

    ved

    fr

    om

    C

    oA

    In E.

    co

    li, A

    CP is

    a se

    para

    te 12

    5-am

    ino

    ac

    id pr

    ote

    in, in

    m

    amm

    als

    it is

    part

    o

    f FA

    S

  • Pho

    spho

    pan

    teth

    ein

    e(P

    an

    t) is

    cova

    len

    tly

    linke

    d vi

    a a

    ph

    osp

    hate

    est

    er

    to a

    se

    rine

    O

    H o

    f th

    e ac

    yl ca

    rrie

    r pr

    ote

    indo

    ma

    in o

    f Fa

    tty Ac

    id Sy

    nth

    ase

    .

    The

    lon

    g fle

    xib

    le ar

    mo

    f pho

    spho

    pan

    teth

    ein

    e

    allo

    ws

    its th

    iol t

    o m

    ove

    from

    o

    ne

    a

    ctiv

    e si

    te to

    an

    oth

    er

    with

    in th

    e

    com

    ple

    x.

    OP

    OH 2

    C

    O

    OCCCNHCH

    2

    CH2

    CNH

    CH3

    H3C

    HH

    O

    O

    CH2

    CH2

    SH

    O

    CH2

    CHNH CO

    -mer

    capt

    oet

    hyla

    min

    e

    pan

    toth

    enat

    e

    se

    rine

    resid

    ue

    phosp

    hopa

    nte

    thei

    ne

    of a

    cyl c

    arrie

    r pr

    ote

    in

    pho

    spha

    te

  • Indi

    vidu

    al s

    teps

    of t

    he Fa

    tty A

    cid

    Syn

    thas

    ere

    act

    ion

    path

    way

    are

    ca

    talyz

    ed by

    the ca

    talyt

    ic d

    om

    ain

    s lis

    ted.

    Fatty

    Aci

    d Sy

    ntha

    se co

    mpl

    ex

    is a

    n obl

    igate

    di

    mer

    .

    With

    in each

    m

    onom

    er,

    th

    e ord

    er

    of e

    nzy

    me do

    main

    s alo

    ng

    the pr

    imar

    y se

    quen

    ceof t

    he pr

    ote

    in is

    sum

    mariz

    ed

    belo

    w.

    There

    is

    stil

    l deba

    te ove

    r th

    e arr

    ange

    ment o

    f dom

    ain

    s in

    3D w

    ithin

    th

    e co

    mpl

    ex.

    An

    ato

    mic

    reso

    lutio

    n st

    ruct

    ure

    of

    the entir

    e co

    mpl

    ex

    has

    not y

    et be

    en ach

    ieve

    d.

    Conde

    nsin

    g M

    alo

    nyl

    /ace

    tyl-C

    oA

    D

    ehyd

    rata

    se En

    oyl

    -K

    eto

    acyl

    A

    CP Th

    ioes

    tera

    se

    Enzym

    e (C

    ys)

    Tran

    sacy

    lase

    (S

    er)

    Re

    duct

    ase

    Re

    duct

    ase

    (P

    ant)

    N-

    -C

    Ord

    er of d

    om

    ain

    s in

    pr

    imar

    y st

    ruct

    ure

    o

    f mam

    mal

    ian

    Fa

    tty A

    cid

    Syn

    thas

    e

  • As e

    ach

    o

    f the

    su

    bstra

    tes

    ace

    tyl-C

    oA

    & m

    alo

    nyl-

    CoA

    bin

    d to

    th

    e co

    mpl

    ex,

    th

    e in

    itia

    l atta

    ckin

    g gr

    ou

    p is

    th

    e o

    xyge

    n o

    f a se

    rine

    hydr

    ox

    ylgr

    ou

    p o

    f the

    Ma

    lon

    yl/a

    cety

    l-Co

    A Tr

    an

    sacy

    lase

    e

    nzy

    me

    do

    ma

    in.

    Each

    a

    cety

    l or

    ma

    lon

    yl m

    oie

    tyis

    tra

    nsi

    en

    tly in

    est

    er

    linka

    ge to

    th

    is se

    rine

    hy

    dro

    xyl,

    befo

    re be

    ing

    tran

    sfe

    rre

    d in

    to th

    ioe

    ste

    r lin

    kage

    w

    ith th

    e

    pho

    spho

    pan

    teth

    ein

    e th

    iolo

    f the

    a

    cyl c

    arr

    ier

    pro

    tein

    (A

    CP) d

    om

    ain

    .

    Ace

    tate

    is

    su

    bse

    que

    ntly

    tra

    nsf

    err

    ed

    to a

    cy

    stei

    ne

    thio

    lof t

    he Co

    nde

    nsi

    ng

    Enzy

    me

    do

    ma

    in.

    Conde

    nsin

    g M

    alo

    nyl

    /ace

    tyl-C

    oA

    D

    ehyd

    rata

    se En

    oyl

    -K

    eto

    acyl

    A

    CP Th

    ioes

    tera

    se

    Enzym

    e (C

    ys)

    Tran

    sacy

    lase

    (S

    er)

    Re

    duct

    ase

    Re

    duct

    ase

    (P

    ant)

    N-

    -C

    Ord

    er of d

    om

    ain

    s in

    pr

    imar

    y st

    ruct

    ure

    o

    f mam

    mal

    ian

    Fa

    tty A

    cid

    Syn

    thas

    e

  • The

    co

    nde

    nsa

    tion

    rea

    ctio

    n (st

    ep

    3) in

    volv

    es

    deca

    rbo

    xyla

    tion

    o

    f the

    m

    alo

    nyl

    mo

    iety

    , fo

    llow

    ed

    by a

    ttack

    o

    f the

    re

    sulta

    nt c

    arb

    an

    ion

    o

    n th

    e

    carb

    on

    yl ca

    rbo

    n o

    f the

    a

    cety

    l (or

    acy

    l) mo

    iety

    .

    Pan

    t

    SH

    Cys

    SH

    Pan

    t

    SH

    Cys

    S C CH3

    O

    Pan

    t

    S

    Cys

    S C CH3

    OC CH

    2

    COO

    O

    Pan

    t

    S

    Cys

    SH

    C CH2

    C

    O

    CH3

    O

    ace

    tyl-S

    -Co

    A H

    S-Co

    Am

    alo

    nyl-

    S-Co

    A H

    S-Co

    ACO

    2

    1 2

    3

    1 M

    alonyl

    /ace

    tyl-C

    oA

    -A

    CP Tr

    ansa

    cyla

    se

    2 M

    alonyl

    /ace

    tyl-C

    oA

    -A

    CP Tr

    ansa

    cyla

    se

    3 Co

    nde

    nsin

    g En

    zym

    e (-

    Ket

    oac

    yl Sy

    nth

    ase)

  • Mec

    han

    ism o

    f ca

    rbo

    n-ca

    rbon

    bo

    nd

    form

    atio

    n in

    fa

    tty

    aci

    d bi

    osy

    nth

    esis

    No

    tes:

    The

    CO2

    that

    w

    as ad

    ded

    in th

    e A

    CC re

    actio

    n

    is lo

    st as

    CO

    2an

    d do

    es n

    ot a

    ppea

    r in

    th

    e fa

    tty ac

    id.

    Loss

    o

    f CO

    2re

    sults

    in

    re

    son

    ance

    -st

    abili

    zed

    carb

    anio

    n

  • 4.Th

    e -k

    eto

    ne

    is

    re

    duce

    d to

    a

    n a

    lco

    hol b

    y e

    tran

    sfe

    r fro

    m N

    ADPH

    .

    5.D

    ehy

    dra

    tion

    yie

    lds

    a tra

    ns

    dou

    ble

    bo

    nd.

    6.R

    edu

    ctio

    n by

    N

    ADPH

    yie

    lds

    a sa

    tura

    ted

    cha

    in.

    Pan

    t

    S

    Cys

    SH

    C CH2

    C

    O

    CH3

    O

    Pan

    t

    S

    Cys

    SH

    C CH2

    HC

    O

    CH3

    Pan

    t

    S

    Cys

    SH

    Pan

    t

    S

    Cys

    SH

    NAD

    PH NA

    DP+

    NAD

    PH N

    ADP+

    C CH HC

    O

    CH3

    C CH2

    CH2

    O

    CH3

    OH

    H 2O

    4 5

    6

    4 -K

    etoac

    yl-A

    CP R

    educt

    ase

    5 -H

    ydro

    xya

    cyl-A

    CP D

    ehyd

    rata

    se

    6 En

    oyl

    -A

    CP R

    edu

    ctas

    e

  • Follo

    win

    g tr

    ansf

    ero

    f the

    gr

    ow

    ing

    fatty

    a

    cid

    from

    pho

    spho

    pan

    teth

    ein

    e to

    th

    e Co

    nde

    nsi

    ng

    Enzy

    me

    's

    cyst

    ein

    e su

    lfhyd

    ryl,

    the

    cy

    cle

    be

    gin

    s a

    gain

    , w

    ith

    an

    oth

    er

    ma

    lon

    yl-Co

    A.

    Pan

    t

    S

    Cys

    SH

    C CH2

    CH2

    O

    CH3

    Pan

    t

    SH

    Cys

    S C CH2

    O

    CH2

    CH3

    Pan

    t

    S

    Cys

    S C CH2

    O

    CH2

    CH3

    C CH2

    COO

    O

    Ma

    lon

    yl-S-

    CoA

    HS

    -Co

    A

    7 2

    7 Co

    nde

    nsin

    g En

    zym

    e

    2 M

    alon

    yl/a

    cety

    l-Co

    A-A

    CP Tr

    ansa

    cyla

    se (re

    peat

    ).

  • Pro

    duct

    re

    leas

    e:

    Whe

    n th

    e fa

    tty a

    cid

    is 16

    ca

    rbo

    n a

    tom

    s lo

    ng,

    a

    Thio

    este

    rase

    dom

    ain

    ca

    talyz

    es

    hydr

    olys

    is o

    f the

    thio

    est

    er

    linki

    ng

    the

    fa

    tty a

    cid

    to

    pho

    spho

    pan

    teth

    ein

    e.

    The

    16

    -C

    satu

    rate

    d fa

    tty a

    cid

    palm

    itate

    is th

    e fin

    al

    pro

    duct

    o

    f the

    Fa

    tty Ac

    id Sy

    nth

    ase

    co

    mpl

    ex.

    Conde

    nsin

    g M

    alo

    nyl

    /ace

    tyl-C

    oA

    D

    ehyd

    rata

    se En

    oyl

    -K

    eto

    acyl

    A

    CP Th

    ioes

    tera

    se

    Enzym

    e (C

    ys)

    Tran

    sacy

    lase

    (S

    er)

    Re

    duct

    ase

    Re

    duct

    ase

    (P

    ant)

    N-

    -C

    Ord

    er of d

    om

    ain

    s in

    pr

    imar

    y st

    ruct

    ure

    o

    f mam

    mal

    ian

    Fa

    tty A

    cid

    Syn

    thas

    e

  • There

    is

    som

    e evi

    dence

    th

    at t

    he 2

    copi

    es

    of t

    he m

    ulti

    -do

    main

    enzy

    me are

    alig

    ned

    antip

    aral

    lel,

    as

    belo

    w.

    In th

    e tra

    nsf

    er

    step

    the gr

    ow

    ing

    fatty

    aci

    d is

    pre

    fere

    ntia

    lly

    pass

    ed

    from

    th

    e AC

    P ph

    osp

    hopa

    nte

    thein

    e th

    iol o

    f one su

    bunit

    to th

    e Co

    nde

    nsi

    ng

    Enzy

    me cy

    stein

    e th

    iol o

    f the

    oth

    er

    subu

    nit

    of t

    he di

    mer.

    How

    ever

    in

    tra-

    subu

    nit

    subs

    trat

    e tr

    ansf

    ers

    also

    occ

    ur.

    Pant-

    SH H

    S-Cy

    s

    Cy

    s-SH

    H

    S-Pa

    nt

    Fatty

    A

    cid

    Synth

    ase

    dim

    er

  • Palm

    itate

    , a

    16

    -C

    satu

    rate

    d fa

    tty a

    cid,

    is th

    e fin

    al

    pro

    duct

    o

    f the

    Fa

    tty Ac

    id Sy

    nth

    ase

    re

    act

    ion

    s.

    Sum

    mar

    y(ig

    no

    ring

    H+

    & w

    ate

    r):ac

    etyl

    -Co

    A +

    7

    mal

    on

    yl-Co

    A +

    14

    NA

    DPH

    palm

    itate

    +

    7

    CO2

    + 14

    NA

    DP+

    + 8C

    oA

    Acco

    un

    ting

    for

    ATP-

    depe

    nde

    nt s

    ynth

    esi

    s o

    f m

    alo

    na

    te:

    8ace

    tyl-C

    oA

    +

    14

    NA

    DPH

    +

    7

    ATP

    palm

    itate

    +

    14

    NA

    DP+

    + 8

    CoA

    +7

    AD

    P+

    7P i

    Fatty

    a

    cid

    syn

    the

    sis

    occ

    urs

    in

    th

    e cy

    toso

    l. Ac

    ety

    l-Co

    A ge

    ne

    rate

    d in

    m

    itoch

    on

    dria

    is

    tra

    nsp

    orte

    d to

    th

    e

    cyto

    sol v

    ia a

    sh

    uttl

    e m

    ech

    an

    ism

    in

    volv

    ing

    citr

    ate.

  • A m

    ole

    cule

    o

    f pa

    lmita

    te co

    sts

    ~13

    6 ATP

    8 ac

    etyl

    ~Co

    A +

    14

    N

    AD

    PH +

    6

    H+

    + 7

    ATP

    pa

    lmita

    te +

    14

    N

    AD

    P++

    8

    CoA

    + 6

    H2O

    +

    7

    AD

    P

    8 ac

    etyl

    ~Co

    A@

    10

    AT

    P/ac

    etyl

    ~Co

    A 80

    AT

    P14

    N

    AD

    PH@

    3.

    5 ATP

    /NA

    DPH

    49 AT

    P7

    ATP

    7

    ATP

    Tota

    l 13

    6 ATP

  • -Oxi

    datio

    n &

    Fatty

    Ac

    id Sy

    nth

    esi

    sCo

    mpa

    red

    Ox

    ida

    tion

    Pa

    thw

    ay

    Fatt

    y A

    cid

    Syn

    thes

    is

    path

    wa

    y lo

    catio

    n

    mito

    cho

    ndr

    ial m

    atrix

    cy

    toso

    l

    acy

    l ca

    rrie

    rs

    (thio

    ls )

    Coen

    zym

    e-A

    pho

    spho

    pan

    teth

    ein

    e (A

    CP) &

    cy

    stei

    ne

    e a

    ccep

    tors

    /do

    no

    r

    FAD

    &

    N

    AD

    +

    NA

    DPH

    -O

    H

    inte

    rmed

    iate

    L D

    2-C

    pr

    odu

    ct/d

    on

    or

    acet

    yl-Co

    A

    mal

    on

    yl-Co

    A

    (& ac

    etyl

    -Co

    A)

  • Fatty

    Ac

    id Sy

    nth

    ase

    is

    tr

    ansc

    riptio

    nal

    ly re

    gula

    ted.

    In liv

    er:

    In

    sulin

    , a

    ho

    rmo

    ne

    pr

    odu

    ced

    whe

    n bl

    oo

    d gl

    uco

    se is

    hi

    gh, st

    imu

    late

    sFa

    tty Ac

    id Sy

    nth

    ase

    exp

    ress

    ion

    .

    Thu

    s e

    xce

    ss gl

    uco

    se is

    st

    ore

    d a

    s fa

    t.Tr

    an

    scrip

    tion

    fa

    cto

    rs th

    at t

    hat m

    edi

    ate

    th

    e

    stim

    ula

    tory

    e

    ffect

    o

    f in

    sulin

    in

    clu

    de US

    Fs(up

    stre

    am

    st

    imu

    lato

    ry fa

    cto

    rs) a

    nd

    SREB

    P-1.

    SREB

    Ps(st

    ero

    l re

    spo

    nse

    e

    lem

    en

    t bin

    din

    g pr

    ote

    ins)

    w

    ere

    fir

    st id

    en

    tifie

    d fo

    r th

    eir

    regu

    latio

    n

    of c

    hole

    ste

    rol s

    ynth

    esi

    s.

    Polyu

    nsa

    tura

    ted

    fatty

    ac

    ids

    dim

    inis

    htra

    nsc

    riptio

    n o

    f the

    Fa

    tty Ac

    id Sy

    nth

    ase

    ge

    ne

    in

    live

    r ce

    lls, by

    su

    ppre

    ssin

    g pr

    odu

    ctio

    n o

    f SR

    EBPs

    .

  • Elo

    nga

    tion

    beyo

    nd

    the

    16

    -C

    len

    gth

    of t

    he

    palm

    itate

    pr

    odu

    ct o

    f Fa

    tty Ac

    id Sy

    nth

    ase

    o

    ccu

    rs in

    mito

    cho

    ndr

    ia a

    nd

    en

    dopl

    asm

    ic re

    ticu

    lum

    (E

    R).

    Fa

    tty a

    cid

    elo

    nga

    tion

    w

    ithin

    m

    itoch

    on

    dria

    invo

    lve

    s th

    e -o

    xida

    tion

    pa

    thw

    ay

    run

    nin

    g in

    reve

    rse

    , e

    xce

    pt th

    at N

    ADPH

    se

    rve

    s a

    s e

    lect

    ron

    don

    or

    for

    the

    fin

    al r

    edu

    ctio

    n st

    ep.

    Po

    lyun

    satu

    rate

    d fa

    tty a

    cids

    e

    ste

    rifie

    d to

    coe

    nzy

    me

    A

    are

    su

    bstra

    tes

    for

    the

    ER

    elo

    nga

    tion

    m

    achi

    ner

    y, w

    hich

    u

    ses

    ma

    lon

    yl-Co

    A a

    s do

    no

    r o

    f 2-ca

    rbo

    n u

    nits

    .

  • Des

    atu

    rase

    sin

    trodu

    ce do

    ubl

    e bo

    nds

    at s

    peci

    fic

    posi

    tion

    s in

    a

    fa

    tty a

    cid

    cha

    in.

    Ma

    mm

    alia

    n ce

    lls a

    re u

    na

    ble

    to

    pr

    odu

    ce do

    ubl

    e

    bon

    ds a

    t ce

    rtain

    lo

    catio

    ns,

    e

    .g.

    , 1

    2 .

    Thu

    s so

    me

    po

    lyun

    satu

    rate

    d fa

    tty a

    cids

    a

    re

    diet

    ary

    esse

    ntia

    ls, e

    .g.

    , lin

    ole

    ic a

    cid,

    18

    :2 ci

    s 9

    ,12

    (18 C

    ato

    ms

    lon

    g, w

    ith ci

    s do

    ubl

    e bo

    nds

    a

    t ca

    rbo

    ns

    9-10

    &

    12-13

    ).

    CO

    OH

    910

    ole

    ate

    18

    :1 ci

    s 9

  • Form

    atio

    n of a

    do

    ubl

    e bo

    nd

    in a fa

    tty a

    cid

    invo

    lves

    the

    follo

    win

    g endo

    plasm

    ic r

    etic

    ulu

    m m

    em

    brane pr

    ote

    ins

    in

    mam

    malia

    n ce

    lls:

    N

    AD

    H-cy

    t b5 R

    edu

    ctas

    e, a fla

    vopr

    ote

    in w

    ith FA

    Das

    prost

    hetic

    gro

    up.

    Cy

    toch

    rom

    e b 5

    , w

    hich

    m

    ay

    be a se

    para

    te pr

    ote

    in or

    a

    dom

    ain

    at o

    ne end

    of t

    he de

    satu

    rase

    .

    D

    esat

    ura

    se, w

    ith an act

    ive si

    te th

    at c

    onta

    ins

    two

    iro

    n

    ato

    ms

    com

    plexe

    d by

    his

    tidin

    e re

    sidu

    es.

    CO

    OH

    910

    ole

    ate

    18

    :1 ci

    s 9

  • The

    de

    satu

    rase

    ca

    talyz

    es

    a m

    ixed

    fu

    nct

    ion

    o

    xid

    atio

    nre

    act

    ion

    .

    The

    re is

    a

    4-

    elec

    tro

    nre

    duct

    ion

    o

    f O2

    2 H

    2Oa

    s a

    fatty

    a

    cid

    is o

    xidi

    zed

    to fo

    rm a

    do

    ubl

    e bo

    nd.

    2e

    pass

    fro

    m N

    AD

    Hto

    th

    e de

    satu

    rase

    vi

    a th

    e

    FAD

    -co

    nta

    inin

    g re

    duct

    ase

    &

    cyto

    chro

    me

    b 5

    , th

    e

    ord

    er

    of e

    lect

    ron

    tra

    nsf

    er

    bein

    g:

    NA

    DH

    FA

    D

    cyt b

    5

    desa

    tura

    se

    2e

    are

    e

    xtra

    cte

    d fro

    m th

    e fa

    tty a

    cid

    as

    the

    do

    ubl

    e

    bon

    d is

    fo

    rme

    d.E.

    g., th

    e o

    vera

    ll re

    act

    ion

    fo

    r de

    satu

    ratio

    n o

    f ste

    ara

    te

    (18:0

    ) to fo

    rm o

    lea

    te (18

    :1 ci

    s 9

    ) is:

    stea

    rate

    +

    N

    AD

    H +

    H

    ++

    O

    2

    ole

    ate

    + N

    AD

    ++

    2H

    2O

  • tric

    arb

    ox

    yla

    te tr

    an

    spo

    rt sy

    stem

    fo

    r tr

    an

    sfer

    o

    fa

    cety

    l Co

    A fr

    om

    m

    itoch

    on

    drio

    n to

    cy

    toso

    l

    Citr

    ate

    ca

    rrie

    s a

    cety

    l gro

    ups

    fr

    om

    th

    e m

    itoch

    on

    drio

    n to

    th

    e cy

    toso

    l fo

    r

    fatt

    y a

    cid

    syn

    thes

    is

    Ace

    tyl~

    CoA

    is ge

    ner

    ated

    in

    th

    e m

    itoch

    on

    drio

    n

    by py

    ruv

    ate

    dehy

    dro

    gen

    ase.

    Ex

    cess

    ac

    etyl

    ~Co

    Ais

    ship

    ped

    to th

    e cy

    toso

    l fo

    r st

    ora

    ge as

    fa

    t.

    Citr

    ate

    is pa

    ssed

    to

    th

    e ct

    yto

    sol.

    ATP-

    citr

    ate

    lyas

    e re

    gen

    erat

    es th

    e ac

    etyl

    ~Co

    A an

    d O

    AA

    in cy

    toso

    l.

    Mal

    ic en

    zym

    e pr

    odu

    ces

    the

    NA

    DPH

    th

    at m

    ay be

    use

    d in

    fa

    tty ac

    id sy

    nth

    esis.

  • Reg

    ula

    tion

    o

    f Fa

    tty

    Aci

    d M

    eta

    bolis

    m

    Fatty

    ac

    id m

    etab

    olis

    m is

    coo

    rdin

    ated

    with

    o

    ther

    as

    pect

    s o

    f met

    abo

    lism

    .

    Ho

    rmo

    nal

    ly re

    gula

    ted

    by pa

    ncr

    eatic

    a an

    d b

    cells

    , w

    hich

    se

    nse

    m

    etab

    olic

    stat

    us

    and

    secr

    ete

    glu

    cago

    n an

    d in

    sulin

    ,

    resp

    ectiv

    ely.

    The

    simu

    ltan

    eou

    s sy

    nth

    esis

    and

    ox

    idat

    ion

    of f

    atty

    ac

    ids

    in liv

    er ce

    lls is

    prev

    ente

    d.M

    alo

    nyl

    ~Co

    A in

    hibi

    ts ca

    rniti

    ne

    palm

    itoyl

    tran

    sfer

    ase

    I.

    Lon

    g te

    rm re

    gula

    tion

    -sy

    nth

    esis

    of A

    CCad

    ipo

    se lip

    popr

    ote

    in lip

    ase,

    an

    d FA

    Sst

    imu

    late

    d by

    in

    sulin

    , in

    hibi

    ted

    by

    glu

    cago

    n, ep

    inep

    hrin

    e.

    A di

    et hi

    gh in

    po

    lyu

    nsa

    tura

    ted

    FA al

    so

    cau

    ses

    decr

    ease

    d FA

    S, A

    CC.