LANJUTAN KARBOHIDRAT

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    KARBOHIDRATKARBOHIDRAT

    DIBAGI 3 GOLONGAN :DIBAGI 3 GOLONGAN :

    1.1. MonosakaridaMonosakarida

    * karbohidrat pain! s"d"rhana* karbohidrat pain! s"d"rhana

    * tidak dapat di#raikan d!n $ara hidroisis* tidak dapat di#raikan d!n $ara hidroisis

    * $ontoh :* $ontoh :

    adosaadosa k"tosak"tosa

    Ato% &3 'triosa( !is"rosa dihidroksias"tonAto% &3 'triosa( !is"rosa dihidroksias"ton

    &)'t"trosa( "ritrosa "ritr#osa&)'t"trosa( "ritrosa "ritr#osa

    & 'p"ntosa( ribosa rib#osa& 'p"ntosa( ribosa rib#osa

    &+ 'h"ksosa( !#kosa ,r#ktosa&+ 'h"ksosa( !#kosa ,r#ktosa

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    G#kosaG#kosa

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    B"da b"nt#k L d!n D pd %onosakaridaB"da b"nt#k L d!n D pd %onosakarida

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    B"nt#k $in$in -iran dan #ranB"nt#k $in$in -iran dan #ran

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    G#!#s K"ton pada MonosakaridaG#!#s K"ton pada Monosakarida

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    /./. DisakaridaDisakarida: t"rdiri dari / %onosakarida: t"rdiri dari / %onosakarida

    ** 0#krosa0#krosa : !#kosa ,r#ktosa : !#kosa ,r#ktosa

    ** LaktosaLaktosa : !aaktosa !#kosa : !aaktosa !#kosa

    ** MatosaMatosa : !#kosa !#kosa : !#kosa !#kosa

    3.3. Oi!osakaridaOi!osakarida: t"rdiri dari 3 2 + %onosakarida: t"rdiri dari 3 2 + %onosakarida

    ).). -oisakarida-oisakarida: + %onosakarida: + %onosakarida

    **A%i#%A%i#%' t"p#n! (' t"p#n! (

    ** Giko!"nGiko!"n poi%"r !#kosa poi%"r !#kosa ** D"kstrinD"kstrin

    ** 0"#osa0"#osa

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    LaktosaLaktosa0#krosa0#krosa

    MaMatosatosa

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    IkatanIkatan 4415) Gikosidik pd 0"obiosa15) Gikosidik pd 0"obiosa

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    B"da Matosa d!n 0"obiosaB"da Matosa d!n 0"obiosa

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    A%i#%A%i#%::

    * M"%p#n6ai rantai #r#s '* M"%p#n6ai rantai #r#s ' ikatanikatan 715) !ikosidik715) !ikosidik( dan( danrantai $aban! 'rantai $aban! ' ikatanikatan 715+ !ikosidik715+ !ikosidik((

    * T"rdapat pada t#%b#h/an : bi8i/an ' padi9b"ras5 !an7* T"rdapat pada t#%b#h/an : bi8i/an ' padi9b"ras5 !an7

    d#%5 8a!#n! d. ( dan #%bi/an ' k"t"a5 #bi5 k"ntan! (d#%5 8a!#n! d. ( dan #%bi/an ' k"t"a5 #bi5 k"ntan! (

    * T"rdiri dari* T"rdiri dari a%iosaa%iosadandan a%iop"ktina%iop"ktin

    Giko!"nGiko!"n

    * str#kt#r spt a%i#%5 rantai $aban! "bih ban6ak* str#kt#r spt a%i#%5 rantai $aban! "bih ban6ak

    * t"rdapat di s" hati dan otot* t"rdapat di s" hati dan otot

    0"#osa0"#osa

    * b"r#pa rantai #r#s '* b"r#pa rantai #r#s ' ikatanikatan 715) !ikosidik715) !ikosidik((

    * %a%aia '%an#sia tidak %"%p#n6ai "ni% s"#as"(* %a%aia '%an#sia tidak %"%p#n6ai "ni% s"#as"(

    * t"rdapat pd dindin! s" tana%an* t"rdapat pd dindin! s" tana%an

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    0tr#kt#r A%i#%0tr#kt#r A%i#%

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    0tr#kt#r Giko!"n0tr#kt#r Giko!"n

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    0tr#kt#r Giko!"n dan A%i#%

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    0tr#kt#r 0"#osa

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    Epimers

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    &arboh6drat"s&arboh6drat"s /=/=

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    H"%ia$"ta > h"%ik"taH"%ia$"ta > h"%ik"ta

    ,or%ation,or%ation

    An ad"h6d" $anAn ad"h6d" $an

    r"a$t ?ith anr"a$t ?ith an

    a$oho to ,or%a$oho to ,or%aa h"%ia$"tah"%ia$"ta..

    A k"ton" $anA k"ton" $an

    r"a$t ?ith anr"a$t ?ith an

    a$oho to ,or%a$oho to ,or%

    aa h"%ik"tah"%ik"ta..

    O &

    H

    R

    OH

    O &

    R

    R@

    OH&

    R

    R@

    O

    aldehyde alcohol hemiacetal

    ketone alcohol hemiketal

    &

    H

    R

    O R@R@ OH

    AR OH AR

    +

    +

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    -"ntos"s and-"ntos"s andh"os"s $anh"os"s $an $6$i"$6$i"as th" k"ton" oras th" k"ton" orad"h6d" r"a$tsad"h6d" r"a$ts?ith a dista OH.?ith a dista OH.

    G#$os"G#$os",or%s an,or%s anintra7%o"$#arintra7%o"$#arh"%ia$"ta5 as th"h"%ia$"ta5 as th"

    &1 ad"h6d" > &&1 ad"h6d" > &OH r"a$t5 to ,or% aOH r"a$t5 to ,or% a+7%"%b"r p6ranos"+7%"%b"r p6ranos"rin!rin!5 na%"d a,t"r5 na%"d a,t"r

    p6ran.p6ran.

    These representations of the cyclic sugars are called

    Haworthprojections.

    H O

    OH

    H

    OHH

    OH

    &H/OH

    H

    OH

    H H O

    OH

    H

    OHH

    OH

    &H/OH

    H

    H

    OH

    -D-glucose -D-glucose

    2

    !

    "

    #

    $ $

    #

    "

    !

    2

    H

    &HO

    & OH

    & HHO

    & OHH

    & OHH

    &H/OH

    $

    "

    2

    !

    #

    D-glucose

    %linear form&

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    &HO

    OHH

    HHO

    OHH

    OHH

    &H/OH

    glucose

    &H/OH

    OHH

    HHO

    OHH

    OHH

    &H/OH

    glucitol

    'a(H!

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    Glycoside Formation

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    Glycosides can be hydrolyzed in aqueous

    acid

    The alcohol obtained after hydrolysis of aglycoside is called an aglycone

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    Oth"r R"a$tions o, Monosa$$harid"sOth"r R"a$tions o, Monosa$$harid"s

    Cnoiation5 Ta#to%"riation and Iso%"riationCnoiation5 Ta#to%"riation and Iso%"riation

    Monosa$$harid"s disso"d in aE#"o#s bas" ?iMonosa$$harid"s disso"d in aE#"o#s bas" ?iiso%"ri" b6 a s"ri"s o, k"to7"no ta#to%"riationsiso%"ri" b6 a s"ri"s o, k"to7"no ta#to%"riations A so#tion o, D7!#$os" $ontainin! $a$i#% h6droid" ?iA so#tion o, D7!#$os" $ontainin! $a$i#% h6droid" ?i

    ,or% s""ra prod#$ts5 in$#din! D7,r#$tos" and D7,or% s""ra prod#$ts5 in$#din! D7,r#$tos" and D7

    %annos"%annos"

    A %onosa$$harid" $an b" prot"$t"d ,ro% k"to7"noA %onosa$$harid" $an b" prot"$t"d ,ro% k"to7"nota#to%"riation b6 $on"rsion to a !6$osid"ta#to%"riation b6 $on"rsion to a !6$osid"

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    or%ation o, Cth"rsor%ation o, Cth"rs

    Th" h6dro6 !ro#ps o, $arboh6drat"s $an b"Th" h6dro6 !ro#ps o, $arboh6drat"s $an b"$on"rt"d to "th"rs b6 th"$on"rt"d to "th"rs b6 th" Fiia%son "th"r s6nth"sisFiia%son "th"r s6nth"sis

    B"n6 "th"rs ar" $o%%on6 #s"d to prot"$t or bo$kB"n6 "th"rs ar" $o%%on6 #s"d to prot"$t or bo$k$arboh6drat" h6dro6 !ro#ps$arboh6drat" h6dro6 !ro#ps

    B"n6 "th"rs $an b" "asi6 r"%o"d b6B"n6 "th"rs $an b" "asi6 r"%o"d b6h6dro!"no6sish6dro!"no6sis

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    Cha#sti" %"th6ation o, %"th6 !#$osid" $an

    b" $arri"d o#t #sin! di%"th6s#,at"

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    Conversion to Esters

    Carbohydrates react with aceticanhydride in the presence of weak

    base to convert all hydroxyl groups to

    acetate esters

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    Conversion to Cyclic cetalsCarbohydrates form cyclic acetals with

    acetone selectively between cis!vicinalhydroxyl groups

    Cyclic acetals from reaction with

    acetone are called acetonides

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    Oidation R"a$tions o, Monosa$$harid"sOidation R"a$tions o, Monosa$$harid"s

    B"n"di$ts or To"ns R"a!"nts: R"d#$in!B"n"di$ts or To"ns R"a!"nts: R"d#$in!0#!ars0#!ars

    Ados"s and k"tos"s !i" positi" t"sts ?h"nAdos"s and k"tos"s !i" positi" t"sts ?h"ntr"at"d ?ith To"ns so#tion or B"n"di$ts r"a!"nttr"at"d ?ith To"ns so#tion or B"n"di$ts r"a!"nt To"ns r"a!"nt A!'NHTo"ns r"a!"nt A!'NH33((//OHJ !i"s a si"r %irror ?h"nOHJ !i"s a si"r %irror ?h"n

    A!A!is r"d#$"d to A!is r"d#$"d to A!==

    B"n"di$ts r"a!"nt 'an akain" so#tion o, $#pri$ $itrat"B"n"di$ts r"a!"nt 'an akain" so#tion o, $#pri$ $itrat"$o%p"( !i"s a bri$k r"d pr"$ipitat" o, $o%p"( !i"s a bri$k r"d pr"$ipitat" o, //OO

    In basi$ so#tion a k"tos" $an b" $on"rt"d to an ados"In basi$ so#tion a k"tos" $an b" $on"rt"d to an ados"

    that $an th"n r"a$t ?ith To"ns or B"n"di$tss r"a!"ntthat $an th"n r"a$t ?ith To"ns or B"n"di$tss r"a!"nt

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    &arboh6drat"s ?ith h"%ia$"ta inka!"s ar"&arboh6drat"s ?ith h"%ia$"ta inka!"s ar"reducing sugarsreducing sugarsb"$a#s" th"6 r"a$t ?ith To"nsb"$a#s" th"6 r"a$t ?ith To"nsand B"n"di$ts r"a!"ntsand B"n"di$ts r"a!"nts

    Th" h"%ia$"ta ,or% is in "E#iibri#% ?ith aTh" h"%ia$"ta ,or% is in "E#iibri#% ?ith as%a a%o#nt o, th" ad"h6d" or k"ton" ,or%5s%a a%o#nt o, th" ad"h6d" or k"ton" ,or%5?hi$h $an r"a$t ?ith To"ns and B"n"di$ts?hi$h $an r"a$t ?ith To"ns and B"n"di$tsr"a!"ntsr"a!"nts

    &arboh6drat"s ?ith on6 a$"ta !ro#ps '!6$osidi$&arboh6drat"s ?ith on6 a$"ta !ro#ps '!6$osidi$

    inka!"s( do not r"a$t ?ith th"s" r"a!"nts and ar"inka!"s( do not r"a$t ?ith th"s" r"a!"nts and ar"$a"d non7r"d#$in! s#!ars$a"d non7r"d#$in! s#!ars

    A$"tas ar" not in "E#iibri#% ?ith th" ad"h6d"A$"tas ar" not in "E#iibri#% ?ith th" ad"h6d"or k"ton" and so $annot r"a$t ?ith th"s"or k"ton" and so $annot r"a$t ?ith th"s"

    r"a!"ntsr"a!"nts

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    "romine #ater$The %ynthesis of ldonic cids

    "romine in water selectively oxidizes thealdehyde group of an aldose to the

    corresponding carboxylic acid

    n aldose becomes an aldonic acid

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    &itric cid 'xidation$ ldaric cids

    (ilute nitric acid oxidizes both the aldehyde

    and primary hydroxyl groups of an aldose toan aldaric acid

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    )eriodate 'xidations$ 'xidative Cleavage of)olyhydroxy Compounds

    Compounds with hydroxyl groups on ad*acentcarbons undergo cleavage of carbon!carbon bonds

    between the hydroxyl groups

    The products are aldehydes+ ketones or

    carboxylic acids

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    #ith three or more contiguous hydroxyl groups+

    the internal carbons become formic acid

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    Cleavage also takes place when a hydroxyl

    group is ad*acent to an aldehyde or ketone

    groupn aldehyde is oxidized to formic acid, a

    ketone is oxidized to carbon dioxide

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    &o cleavage results if there are intervening

    carbons that do not bear hydroxyl or carbonylgroups

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    -eactions of .onosaccharides with

    )henylhydrazine$ 'sazones

    n aldose or ketose will react with threeequivalents of phenylhydrazine to yield a

    phenylosazone

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    -eaction of (!Glucose or (!.annose with excess

    phenylhydrazine yields the same phenylosazone/

    Therefore+ (!glucose and (!mannose differ in

    configuration only at C0/Compounds that differ in configuration at only one

    stereogenic center are called epimers/

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    %ynthesis and (egradation of .onosaccharides

    1iliani!Fischer %ynthesisThe carbon chain of an aldose can be extended by$

    ddition of cyanide to epimeric cyanohydrins

    2ydrolysis to a mixture of epimeric aldonic acids

    or aldonolactones-eduction of the epimeric aldonic acids or

    aldonolactones to the corresponding aldoses

    For example+ (!glyceraldehyde can be converted to

    (!erythrose and (!threose by the 1iliani!Fischersynthesis

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    Th R ,, D d tiTh R ,, D

    d ti

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    Th" R#,, D"!radationTh" R#,, D"!radationAn ados" $an b" short"n"d b6 on" $arbon ia:An ados" $an b" short"n"d b6 on" $arbon ia:

    Oidation ?ith bro%in" ?at"r to th" adoni$ a$idOidation ?ith bro%in" ?at"r to th" adoni$ a$id

    Oidati" d"$arbo6ation ?ith h6dro!"nOidati" d"$arbo6ation ?ith h6dro!"np"roid" and ,"rri$ s#,at"p"roid" and ,"rri$ s#,at"

    & i , d i t it

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    &on"rsion o, an ados" into its&on"rsion o, an ados" into its

    "pi%"r"pi%"r)H*

    )H2*H

    H *H

    *H H

    H *H

    H *H

    D-+lucose

    (r2,H

    2*

    )**H

    )H2*H

    H *H

    *H H

    H *H

    H *H

    pimeriation

    '

    )**H

    )H2*H

    *H H

    *H H

    H *H

    H *H

    )lH

    lactoniation

    *

    )H2*H

    *H H

    *H H

    H

    H *H

    *'a,Hg H

    2*

    pH -"

    )H*

    )H2*H

    *H H

    *H H

    H *H

    H *H

    D-+luconic acid D-/annonic acid

    D-/annose

    & ,& i , k t h i t

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    &on"rsion o, a k"toh"os" into an&on"rsion o, a k"toh"os" into an

    adoh"os"adoh"os")H

    /*H

    )H/*H

    *

    *H H

    H *H

    H *H

    'a(H!

    or H20 1t

    )H/

    *H

    )H/*H

    *H H

    *H H

    H *H

    H *H

    /annitol

    )H/

    *H

    )H/*H

    H *H

    *H H

    H *H

    H *H

    +lucocitol0 oror3itol

    D-4ructose

    controlledo5idation 3y dil.

    nitric acid

    )**H

    )H2*H

    H *H

    *H H

    H *H

    H *H

    D-+luconic acid

    )**H

    )H2*H

    *H H

    *H H

    H *H

    H *H

    D-+lucose

    )lH

    lactoniation

    *

    )H2

    *H

    *H H

    *H H

    H

    H *H

    * 'a,Hg H2*

    pH -"

    )H*

    )H2

    *H

    *H H

    *H H

    H *H

    H *H

    D-/annose

    *

    )H2*H

    H *H

    *H H

    H

    H *H

    *

    )H*

    )H2

    *H

    H *H

    *H H

    H *H

    H *H

    & i , d h i t& i , d h i t

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    &on"rsion o, an adoh"os" into&on"rsion o, an adoh"os" into

    k"toh"os"k"toh"os"

    )H/*H

    %)H*H&n

    )H/*H

    )H*

    1 )+H*'H'H/

    )+H

    *''

    )+H

    *'H'

    %)H*H&n

    )H/*H

    H

    H

    6 l d o s e

    1 h e n y l h y d r a . i n e

    1 h e n y l o s a . o n e

    )H*

    /

    %)H*H&n

    )H/*H

    )H*

    * 7n, 6cetic acid

    * s o n e

    %)H*H&n

    )H/*H

    )H/*H

    *

    8 e t o s e

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    Too much ..

    Carbohydrate will be convertedinto fat and stored under theskin leading to weight gain!

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    TCRIMAKA0IHTCRIMAKA0IH