LANJUTAN KARBOHIDRAT
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Transcript of 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