CarbohydraLes

Nomeoclotote
cotbobyJtotes ote byJtotes of cotboo
- Monosaccharldes (slmple sugars) cannoL be
broken down lnLo slmpler sugars under
mlld condlLlons
- Cllgo a few usually 2 Lo 10
- olysaccharldes are polymers of Lhe slmple
sugars
,ooosoccbotlJes
- Aldoses and keLoses conLaln aldehyde and
keLone funcLlons respecLlvely
- 1rlose LeLrose eLc denoLes number of carbons
- Aldoses wlLh 3C or more and keLoses wlLh 4C or
more are chlral
AIdoses cIassification
etoses cIassification
teteocbemlstty
- SLereolsomers LhaL are mlrror lmages of each
oLher are enanLlomers
- alrs of lsomers LhaL have opposlLe conflguraLlons
aL one or more chlral cenLers buL are nC1 mlrror
lmages are dlasLereomers
- 1wo sugars LhaL dlffer ln conflguraLlon aL only one
chlral cenLer are eplmers
cycllc moosoccbotlJe sttoctotes
ooJ ooometlc fotms
- Clucose (an aldose) can cycllze Lo form a
cycllc hemlaceLal
- lrucLose (a keLose) can cycllze Lo form a
cycllc hemlkeLal
- Cycllc form of glucose ls a pyranose
- Cycllc form of frucLose ls a furanose
cyc/isotion ond conformotion
1he |ength and the va|ency ang|es of the|r carbon atoms causes
pentoses and hexoses to form rinqs
|e they cyc/ise
1he r|ngs become stab|e because
a|dehydes (||ke C1 of g|ucose) can add hydroxy| groups to the|r
carbony| group the stra|ghtcha|n (or open cha|n) hexoses can
thus add a Cn from one of the asymmetr|c carbons w|th|n the|r
mo|ecu|e to C1
1hese r|ngs conta|n oxygen and are named as der|vat|ves of the s|x
membered pyran
eg g|ucose (a|dohexoses) and f|ve membered furan r|ng systems
eg fructose (ketohexoses)
G|ucose forms a s|x membered r|ng and can be ca||ed
g|ucopyranose
Iructose forms a f|ve membered r|ng and can be ca||ed
fructofuranose
O
O
n soIution an equiIibrium exists
between open (straight) and
cIosed (ring) forms
cyc/isotion ond conformotion
1h|s cyc||sat|on |eads to the appearance of yet another
asymmetr|c carbon (C1)
Depend|ng on wh|ch way the r|ng forms about th|s carbon the
structure |s ca||ed an - or . conformotion 1he two forms are
ca||ed onomers and C1 becomes the anomer|c carbon
1he anomers |nterconvert by a process ca||ed mutorototion a
r|ng formed |n one conformat|on can open and c|ose aga|n |n
the other conformat|on
Another draw|ng method noworth projection |s used to show
these cyc||sed mo|ecu|es
nere the subst|tuents on the carbon atoms are represented as
extend|ng obove or be/ow the p|ane of the rinq - |nd|cates
that the anomer|c C1 hydroxy| group |s be/ow the p|ane of the
r|ng and . |nd|cates that |t |s obove the p|ane of the r|ng
Mu1A8C1A1lCn
n soIution an equiIibrium exists
between open (straight) and
cIosed (ring) forms
Rings may form in -
or .conformations
cycllc moosoccbotlJe sttoctotes
ooJ ooometlc fotms
- Cycllc forms possess anomerlc carbons
- lor usugars alpha has CP down beLa has
CP up
- lor Lsugars Lhe reverse ls Lrue
noworth projections
-DG|ucose .DG|ucose
O
H
OH
H OH
H
H
OH
OH
CH
Z
OH
O
OH
H
H OH
H
H
OH
OH
CH
Z
OH
%he 3-dimensionaI arrangement is not reaIIy fIat Iike
they are shown here.
Chalr 8oaL
t is more reaIistic to envisage
substituent -H and -OH groups as
parallel or perpendicular to the pIane
of the sugar ring.
A paraIIeI (striped) or perpendicuIar
(black) reIationship affects the
stabiIity of the moIecuIe.
Such moIecuIes can exist in two
interconvertabIe conformations, the
chair and the boat
Chair is the conformation with the
most substituent groups in the
paraIIeI conformation is the more
stable.
,ooosoccbotlJe uetlvotlves
- 8educlng sugars sugars wlLh free anomerlc
carbons Lhey wlll reduce oxldlzlng agenLs
such as peroxlde ferrlcyanlde and some
meLals (Cu and Ag)
- 1hese redox reacLlons converL Lhe sugar Lo a
sugar acld
- Clucose ls a reduclng sugar so Lhese
reacLlons are Lhe basls for dlagnosLlc LesLs for
blood sugar
iabetic patients - gIucose measurement
n glucometer strips, glucose oxidase is coated.
When microlitre volume of blood spotted on the strip, it gets oxidised.
Glucono-lactone and hydrogen peroxide are released.
ClycosylaLed Pemoglobln (PbA1C)
W Why Lo measure mean blood glucose conc?
W ?our before meal (ac) and posLprandlal (afLer
food pc) sugar ls varlable 1o geL a conslsLenL
value go for PbA1c (sLays sLable for 2 monLhs)
W When blood glucose enLers 88C lL glycosylaLes
epsllon group of Lyslne and amlno Lermlnal
Pemoglobln
W Palf llfe of 88C ls 60 days
W Mean PbA1c level ls 63 lf you exceed 7 you
have Lo be waLchful on your dleL llfesLyle (couch
poLaLoes)!
,ote ,ooosoccbotlJe
uetlvotlves
- Sugar alcohols mlld reducLlon of sugars
- ueoxy sugars consLlLuenLs of unA eLc
- Sugar esLers phosphaLe esLers llke A1 are
lmporLanL
- Amlno sugars conLaln an amlno group ln place
of a hydroxyl group
- AceLals keLals and glycosldes basls for ollgo
and polysaccharldes
llqosoccbotlJes
- 8e able Lo ldenLlfy anomerlc carbons and
reduclng and nonreduclng ends
- Sucrose ls nC1 a reduclng sugar
- noLe carefully Lhe nomenclaLure of llnks! 8e
able Lo recognlze alpha(14) beLa(14)
OLl6O54ccn4klu5
W 1wo monosacchar|des are g|ycos|d|ca||y ||nked to
form a disacchar|de
W |m||ar|y tri tetro pento and hexosacchar|des are
formed by [o|n|ng three four five ond six
monosacchar|des respect|ve|y
W 1he pref|x o/iqo means 'hav|ng a on|y few'
W A pentasacchar|de has on|y a few monosacchar|des
|n |t (actua||y |t has f|ve)
An - g|ycos|d|c bond
4 1 4 1 4 1 4 1
O
OH OH
C
+
O
OH OH
C
O
OH
C
O
OH
C
O
ecause the OH on both C1 and C4 are beIow the pIane of the
ring an --1, 4 bond has been formed here.
,a|tose
g|ucose -(1 4)g|ucose
O
OH
CH
Z
OH
O
OH
CH
Z
OH
O

4
3
Z
OH
OH
1
4
Z
3
OH
1
OH
Non-reducing
Curbon C4
Reducing Curbon C1
u-1 4 gIycosidic bond
A reducing disaccharide with an -(1,4) gIycosidic Iinkage.
actose
ga|actose .(1 4)g|ucose
Note d|fference between g|ucose and ga|actose
Cn or|entat|on on C4
O
CH
Z
OH
O
OH
CH
Z
OH
OH
OH
OH
OH
Non-
reducing
Curbon C4
Reducing Curbon C1 O
A reducing disaccharide with a .(1,4)gIycosidic Iinkage.
OH
.-1 4 gIycosidic bond
ucrose
g|ucose -(1 2).fructose
ote the reducing carbons on both gIucose (C1) and fructose
(C2) are invoIved in the gIycosidic bond and consequentIy
sucrose is not a reducing sugar.
O
OH
CH
Z
OH
CH
Z
OH
O
OH
OH
OH
Non-
reducing
Curbon
C4
Reducing Curbon CZ
CH
Z
OH
O
OH
A non-reducing
disaccharide
with an -(1, 2). gIycosidic
Iinkage.
Reducing Curbon C1
9olysoccbotlJes
looctloos stotoqe sttoctote tecoqoltloo
- nomenclaLure homopolysaccharlde vs
heLeropolysaccharlde
- SLarch and glycogen are sLorage molecules
- ChlLln and cellulose are sLrucLural molecules
- Cell surface polysaccharldes are recognlLlon
molecules
9OLY54ccn4klu5
W 9o|ysacchar|des have a h|gh mo|ecu|ar we|ght
W Composed of many s|mp|e or der|ved
monosacchar|des connected by g|ycos|d|c bonds
W In 8|o|ogy the most common bu||d|ng b|ock |s u
q/ucose
W 9o|ymers composed of a s|ng|e type of bu||d|ng
b|ock are ca||ed homopo/ymers
W 9o|ymers composed of more than one type are
ca||ed heteropo/ymers
9OLY54ccn4klu5
5toroqe of chem|ca| energy eg starch
(p|ant ce||s) and g|ycogen (an|ma| ce||s)
W G|ucose stored as g|ycogen po|ymer reduces the
osmot|c pressure of stored sugars
W G|ycogen |s found |n the cytoso| as dense granu|es
wh|ch conta|n g|ycogen and the enzymes |nvo|ved
|n both |ts synthes|s and mob|||sat|on
W G|ycogen granu|es are most abundant |n ||ver and
musc|e ce||s
9OLY54ccn4klu5
W 8oth starch and g|ycogen are -(1 4) homopo/ymers
w|th occas|ona| -(1 6) ||nkages to make branch
po|nts
W G|ycogen |s more hiqh/y bronched
-(1 6) ||nkage occurr|ng every 8 to 10 g|ucose un|ts
g|v|ng r|se to short branch cha|ns of about 812
g|ucose un|ts
W tarch occurs |n branched and unbranched forms
-(1 6) bronches occur /ess frequent/y a|ong the
mo|ecu|e (once every 122S g|ucose res|dues) and
g|ve r|se to |onger branch cha|ns (202S g|ucose
un|ts) than |n g|ycogen
lycoqeo
1be qlocose stotoqe Jevlce lo oolmols
- Clycogen consLlLuLes up Lo 10 of llver mass
and 12 of muscle mass
- Clycogen ls sLored energy for Lhe organlsm
- Cnly dlfference from sLarch number of
branches
- Alpha(16) branches every 812 resldues
- Llke amylopecLln glycogen glves a redvloleL
color wlLh lodlne
GCCGLN ] 1AkCn
tarch has -(1 4)g|ucose repeat|ng un|t
G|ycogen has -(1 6)g|ucose branch po|nt
O
OH
CH
Z
OH
O
OH
O
CH
Z
O

4
3
Z
OH
OH
1
4
Z
3
OH
1
OH
Non-reducing
Curbon C4
Reducing Curbon C1
CH
Z
OH
O
OH
OH
OH
Reducing
end huving
u free C1
- 1 brunch
points
- 14
struight
chuin
bonds
SLYCOSEN
runching
W increuses soIubiIity
W increuses the rute of both synthesis
und degrudution
W Non-reducing ends {=C4} ure sites of
synthesis und degrudution
Non-reducing ends
huving u free C4
totcb
A ploot stotoqe polysoccbotlJe
- 1wo forms amylose and amylopecLln
- MosL sLarch ls 1030 amylose and 7090
amylopecLln
- 8ranches ln amylopecLln every 1230
resldues
- Amylose has alpha(14) llnks one reduclng
end
totcb
A ploot stotoqe polysoccbotlJe
- Amylose ls poorly soluble ln waLer buL
forms mlcellar suspenslons
- ln Lhese suspenslons amylose ls hellcal
lodlne flLs lnLo Lhe hellces Lo produce a blue
color
by btoocbloq lo totcb?
cooslJet tbe pbospbotylose teoctloo
- hosphorylase releases glucose1 producLs
from Lhe amylose or amylopecLln chalns
- 1he more branches Lhe more slLes for
phosphorylase aLLack
- 8ranches provlde a mechanlsm for qulckly
releaslng (or sLorlng) glucose unlLs for (or
from) meLabollsm
uexttoos
A smoll bot slqolflcoot Jlffeteoce ftom stotcb
ooJ qlycoqeo
- lf you change Lhe maln llnkages beLween
glucose from alpha(14) Lo alpha(16) you
geL a new famlly of polysaccharldes
dexLrans
- 8ranches can be (12) (13) or (14)
uexttoos
A smoll bot slqolflcoot Jlffeteoce ftom stotcb
ooJ qlycoqeo
- uexLrans formed by bacLerla are
componenLs of denLal plaque
- Crossllnked dexLrans are used as
Sephadex gels ln column chromaLography
- 1hese gels are up Lo 98 waLer!
ttoctotol 9olysoccbotlJes
composltloo slmllot to stotoqe
polysoccbotlJes bot smoll sttoctotol
Jlffeteoces qteotly lofloeoce ptopettles
- Cellulose ls Lhe mosL abundanL naLural
polymer on earLh
- Cellulose ls Lhe prlnclpal sLrengLh and
supporL of Lrees and planLs
- Cellulose can also be sofL and fuzzy ln
coLLon
5tructuro/ mo|ecu|es eg ce||u|ose
W Average ,r S0000
W ,any g|ucose mo|ecu|es connected by .14 ||nks a
cha|n
2000 cha|ns 1 m|crof|br||
W 8ecause of .14 ||nks a|ternat|ng res|dues f||pped
through 180 degree re|at|ve to each other nbonds
stab|||se th|s g|v|ng a /ineor secondary structure
W 9o|ymer cha|ns have a h|gh aff|n|ty for each other
and form para||e| bund|es
ttoctotol 9olysoccbotlJes
composltloo slmllot to stotoqe
polysoccbotlJes bot smoll sttoctotol
Jlffeteoces qteotly lofloeoce ptopettles
- 8eLa(14) llnkages make all Lhe dlfference!
- SLrands of cellulose form exLended rlbbons
cLLuLO5
g|ucose .(1 4)g|ucose repeat|ng un|t
Cn
Cn
O
CH
Z
OH
O
OH
CH
Z
OH
OH
OH
OH
OH
Non-
reducing
Curbon C4
Reducing Curbon C1 O
CELLULOSE SECOARY S%RUC%URE
s Iinear
Long straight chains
occur in cellulose
because of the .(1, 4)
configuration
In starch, the -(1, 4)
configuration, the chain has a
natural curvature and a helix is
formed,
tbet ttoctotol 9olysoccbotlJes
- ChlLln exoskeleLons of crusLaceans lnsecLs
and splders and cell walls of fungl
slmllar Lo cellulose buL C2s are naceLyl
cellulose sLrands are parallel chlLlns can be
parallell or anLlparallel
tbet ttoctotol 9olysoccbotlJes
- AlglnaLes Cablndlng polymers ln algae
- Agarose and agaropecLln galacLose
polymers
- Clycosamlnoglycans repeaLlng
dlsaccharldes wlLh amlno sugars and
negaLlve charges
ome b|o|og|ca||y |mportant po|ysacchar|des
cons|st of sugars other than g|ucose or |ts
der|vat|ves eg ch|t|n found |n the she||s of
crustaceans and |nsects |s a ||near .(14)
po|ymer of Nacety|Dg|ucosam|ne
neteropo/ymers conta|n two or more d|fferent
sugars |n stra|ght or branchedcha|n ||nkages
eg g|ycosam|nog|ycans found |n the
extrace||u|ar matr|x of mu|t|ce||u|ar organ|sms
HETEROPOLYMERS
Carbohydrate heteropo|ymers can be
assoc|ated w|th prote|ns |n a number of ways
to produce
W proteoq/ycons
Moin/y suqor w|th some prote|n are structura|
e|ements |n ce|| wa||s of bacter|a
W q/ycoproteins
Moin/y protein w|th some sugars (130)
found |n p|asma membranes |nvo|ved |n ce||
s|gna|||ng and recogn|t|on eg b|ood group
ant|gens
Clycosamlnoglycans
(CACS)
W CACS are exLracellular heLeropolysaccharldes
W resenL ln LxLracellular MaLrlx (LCM)
W 8epeaLlng dlsaccharlde unlLs
W Cne unlL ls uronlc acld/lduronlc acld and Lhe
oLher unlL ls nAC (naceLyl glucosamlne/
galacLosamlne)
W resence of Lwo sulfaLe groups ln heparln
glves Lhem hlgh denslLy negaLlve charge Lo
adopL exLended conformaLlons
CACS
1 Pyaluron
2 ChondrolLln 4sulfaLe
3 uermaLan sulfaLe
4 keraLan sulfaLe
3 Peparln sulfaLe
1 Pyaluronan
W Clucuronlc acld + naceLyl glucosamlne (nAC)
W 30000 dlsaccharlde repeaLs
W 8eLa 13 llnkage
W AcLs as lubrlcanLs ln synovlal [olnLs vlLreous
humor of eye
W rovldes Lenslle sLrengLh and elasLlclLy Lo
Lendons caLllages
W Pyaluronldase hydrolyzes hyaluronan Lo make
Lhe Llssue sofLer for bacLerlal lnvaslon
W Also Lhe enzyme helps sperm Lo enLer Lhe
ovum by hydrolyzlng Lhe ovum coaL
W Pyaluronan ls a long polymer MolwL of
several mllllon
2 ChondrolLln sulfaLe
W Clves Lenslle sLrengLh Lo carLllage Lendons
llgamenLs and aorLa walls
W Clucuronlc acld + naceLyl galacLosamlne 4
sulfaLe
W 8eLa 13 llnkage
3 keraLan sulfaLe
W Absence of uronlc acld
W resenL ln cornea bone horn hoof halr nalls
and claws
W CalacLose + naceLyl glucosamlne (6sulfaLe)
W 8eLa 14 llnkage 8eLa 13 llnkage
4 uermaLan sulfaLe
W ConLrlbuLes Lo pllablllLy of skln presenL ln
blood vessels and hearL valves
W lduronlc acld ls presenL
3 Peparln sulfaLe
W lduronaLe (2sulfaLe) + naceLyl glucosamlne (3S
and 6S)
W Alpha 14 llnkage
W lnhlblLs coagulaLlon by blndlng Lo Lhe proLease
lnhlblLor anLlLhrombln
W AnLlLhrombln lnhlblLs Lhe blood cloLLer Lhrombln
W Peparln ls hlghly elecLronegaLlve and so
elecLrosLaLlc lnLeracLlon
Clycocon[ugaLes
W 1 proLeoglycans
W 2 glycoproLelns
W 3 glycollplds
1 roLeoglycans
W Core proLeln unlL has covalenLly aLLached CACS
by LeLrasaccharlde brldge
W 1he polnL of aLLachmenL ls serlne
W SerClyxCly
W 1wo ma[or groups syndecans glyplcans
W Syndecans have slngle Lransmembrane domaln
wlLh Lhree Lo flve heparln sulfaLe/chondrolLln
sulfaLe
W Clyplcans are aLLached Lo membrane by
phosphaLldyllnoslLol llpld anchor
roLelnproLeln lnLeracLlons wlLh
Peparan sulfaLe
1 conformaLlonal acLlvaLlon
2 enhanced proLelnproLeln lnLeracLlon
3 corecepLor for exLracellular llgands
4 cell surface locallzaLlon
roLeoglycan aggregaLes wlLh
many aggregan
2 ClycoproLelns
- CarbohydraLesproLeln con[ugaLes
- May be nllnked or Cllnked
- nllnked saccharldes are aLLached vla Lhe
amlde nlLrogens of asparaglne resldues
- Cllnked saccharldes are aLLached Lo hydroxyl
groups of serlne Lhreonlne or hydroxylyslne
- Lxample of Cllnked glycoproLeln ls mucln
lqolflcooce of O/NllokeJ
lycoptotelos
- luncLlon ln many cases ls Lo adopL an
exLended conformaLlon due Lo hlgh negaLlve
charges
- Pydrophlllc clusLers of carbohydraLes alLer
Lhe solublllLy of con[ugaLed proLelns
- Pelps ln proLeln quallLy conLrol LransporL
degradaLlon
- roLecLlon from proLeolyLlc enzymes
3 Clycollplds
W CarbohydraLellpld con[ugaLlon
W eg gangllosldes polar head group ls slallc acld
(naceLylneuramlnlc acld)
W Cllgosaccharldes deLermlne human blood
groups
kLCC,,LNDLD kLADING
names and nooper
Instants Notes |n 8|ochem|stry 5ection l
Ne|son Cox (ehn|nger's)
9r|nc|p|es of 8|ochem|stry
8erg 1|moczko tryer
8|ochem|stry V chopters 11 14 1 21