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CARBOHYIIRATES
Isomerism is the existence of two or more compounds with the same composition
(same number and kind of atoms, i.e., same molecular weight) but different constitution
(different manner in which the atoms are joined together aJrepresented by the structural
formula).
A' STRUCTURAL ISOMERS have the same molecular formul4 but different attachments
1. Skeletal or chain isomers, e.9., n-butane and isobutane
cH3-cH2-cH2-CH3 cH3-cH-cI{3
I
CH3
CI
85 BIOCHEMISTRYfOTNURSINGSTUDENTS
STEREOISOMERS
1. Geometric or cis-trans isomerism, e.g., furnalic acid and malelc acid
H-C_COOH H_C_COOH
lt
ll il
HOOC-_HC H-C-COOH
2. Optical isomers
s that a. Enantiomers or optical antipodes are mirror images of each other (chiral)
w0 0r and non-superimposable. They have the same melting Point,(iutp), boiling
lution point (BP) and solubility, but they rotate plTe polarized lig]'t in different
I.rntes, ' directions. Hence, enantiomers are either dextro-rotatory (6-) and rotates
s nnd plane polarized light to the right; or levorotatory ( 1- ) Td lotates plang
polarized light to [-,. t"ft. NotJthat the notations D- and L- are not
related
it applies to position of the
to the direci.on of rotation of light. f*ather, lhe
as compared with the standard, D(+)
l - oH of the penultimatu .urbon atom' and
gfy."ruld.hyde ( -OH written t9 F".right il,P" central carbon
is
:,lirril -CHO on top). The structure of D-glyceraldehyde
-. , i,--,r',
, -.r al CHO
\
cH20H
b.DiastereomersarenotmirrorimagesofeachoF"''Theyhavedifferent
MR BP and solubiiities, e'g' erythrose
H_C-OH HO-C-OH
I
H-C_OH HO-C-H
1
HO_C_H H-C-OH
I
cH2oH
I
cH2oH
ll
cH2oH cH,oH
I II III IV
I and I1 are enantiomels, III ancl IV are enantiomers, but I is the diastereorrter
of III and iV.
87
-....'.:{!ITE
Examplel. CH]-CH2-CH-CHl 2-ctrloro-butane or butyl chloride
I
C1
I CrHo
T,',
Ii __-_
I
Ct c,fH
CH, CH,
(-) sec. butyl chloride (+) sec. butyl chloride e
(
2. CH3-CI{*-CH*-CHr--CH,
Exarnple
tl
Cl Cl
S
?3, dichloropentane
Note: asterisk marks the chiral carbons
CH, CH, CH, CH,
H -fcr cr-l- u u -]- cr cr -l- H
cl-f- I
H H -]- c1 H -l- cl
I
cr -]- H
I
H --l-cl
._-L_
cr-f u \/\/
rt
-+--cr
H---
planes of
CH, CH, CH, CH,
syrnmetry
I iI IIi IV
In2,3, dichlorobutane, I and II are enantiomers, but III and IV are meso compounds
and are not optically active. However, meso compounds iII and IV are diastereomersbf both
I and II.
#
ffi
ffi It must also be noted that there are molecules with no.chiral centers which exhibit
ffi optical activity. Examples are
ffi u,NQQ NH, CFIr,.O = CHCOOH
ffi
ffi
3,3' diaminospiro(3,3,heptane) and 4-methyl cyclohexylidene acetic acid
ffi
ffi ' The configuration of a molecule may be absolute (refers to the actual arrangement of
ffi atoms or groups of atoms- as determinecl by X-ray diffraction techniques) or relative
(deterrninedby comparison with the configuration of a standard). D(+) glycbraldehyde is the
tr
tt standard for carbohydrates.
tr
$
,l
i:
HO-C-H
I
H-C-OH
I t'
C:O
i I i l
HO-q-H
I
H-C-OH
I I
H-C-OH
I I
H-C_OH
I
H-C_OH H-C-OH
I L
I
All 4 sugars are D- sugars because they have the same configuration as D-
glyceraldehyde on the penultimate carbory C-5.
J. The 3 aldohexoses are not mirror images of each other, hence they are
diastereomers.
4. There are 4 chiral carbons, hence there are 16 expected optical isomers, i"e., eight
pairs of euanliomers.
89
Apparently, a special type of diastereomerism exists in
a.) Skeletal or structural functionsl e ,g.r cellulose, the major structural component
of plant cell walls; and peptidoglycans of bacterial cell walls.
$
$,
,&
$h There are evidences to support the belief that other forms of glucose, in addition to
Itil
s; the open chain form, are present- Among these evidences are:
$ 1 . Simple aldehyd es und ergo the Kiliani-Fischer symthesis (a reaction that increases
xi the chain length of a molecule by generating a new asy'mmetric carbon) easily.
Aldohexoses undergo this reaction with difficulty.
.if
;i
2. Glucose and other aldoses fail to give a positive Schiff's test (magenta color
ii. with Schiff's reagent) given by most aldehydes.
ril
:!
iii
i
'i 3. Glucose is relatively inert to O, whereas aldehydes are notoriously auto-
t oxidizable.
j
:;
4. Glucose exhibits mutarotation, i.e., there are two crystalline forms of glucose.
; D glucose crystaliized from water gives a-D glucose whose I a ] = +113"
whereas D glucose crystallized from acetic acid or pyridine yields b-D
glucosewithIa] = +19''
This structural abnormality is explained by the ability of aldohexoses to react internally
to form cyclic hemiacetals. This becomes possible due to the proximity of an.alcoholic -OH
on C-5 to the CHO group at C-1.
o
R-C-H + R'-OH
l1
OH
When C-1 reacts with the -OH at C-5 to form a 5-membered ring, the suffix -pyranose
is used. \A4ren C-1 reacts with C-4 to form a S-membered ring, the suffix is -furanose.
$
$
H H
tr
$
fr /\
cH._o c-c
//\
$ HC CH H CC H
ft
\^/
H H \/
o
Pyran furan
Alpha:rnomer Beta anomer
All bulky groups except the All bulky groups are equatorial, and are
anomeric -OH are equatorial, and written below the plane of the ring.
are written above the plane of the ring.
An equilibrlum exists between the alpha form (36%), the beta form (67'h), and
the open chain form of glucose (1%).
2. The alpha and beta forms differ only in the position of -H and -OH at C-1 and
are called :rnomers.
6 6 6
cHroH H cH2oH
o( ^,
4 1c=0
HO
r CH"OH
cH,oH
H -c;oH o
i'l
HO- ?H HO -C;H IIr .ro-J-r,
l'l I
I
H- ,* oH H -C------ ------l c-n
l* l4
I
H- H-C-OH
I
H -C-5 OH eH,
l
I
cH,oH cH,oH
b
C. Haworth formulas
6
OH,
(4
H
J" ,!' 2
H_C-OII
I
cr{2oI'I
g - D-Cluco- - L-Arabino
cv" - D-Clucose
furanose
'cr -furanose
D-Galacto B
py1'anose
f
Pyranose I
:,j*
ti'
93
*;/
1. Monosaccharides exhibit mutarotation (form o and B anomers).
2. When these sugars act as reducing agents, they are in turn oxidized
mild OAs aldonic acids
(C-1 -------+ COOH)
s\rong ONs, e.9.,\lNO3
glucose aldaric acids
(cHo&c-6-cooH)
CNZVMES
uronic acids
( C-6.--.--.+ COOH)
J. The aldehyde and ketone functions may be reduced to sugar alcohols, e.g.,
H? Pt or I'JnBHo fermentation
Glucose D-sorbitol sorbose ascorbic
nerobncter ---.,!- acid
suboxy dans (a keto-sugar)
CHrl or
glucose penta- O -methyl 2, 3, 4,6 tetraO- -
(cH)2so4
B-D glucose --.r- methyl D-glucose
HoCI{,(CHoH)1CHo iF ro.rr,-?."o
94 BIOCTiCNISTiYTOTNURSINGSTUDENTS
Tests Reagents & Product Positive
Procedures Responsible Result
for Color
Molisch test o naphthol, then heat Furfural and Violet dng
with concentrated hydroxy furfural
HrSOi, generai test
for carbohydrates
orcinol, 30% l{Cl
FeCl, solution
Bial's Orcinol Presence of pentoses Formation of Trioses, uronic
test & nucleotides with furfural (pentoses) acids, heptoses
pentoses & hydroxyfurfural give blue or
(hexoses) which gleen products,
yields blue green hexoses give
compound in the yellow brovrm
presence of Fe*3 products
ions
Seliwanoff 's HCl + resorcinol Dehydrated Bright cherry red
test differentiates ketoses react with ketohexose,
aldohexoses from faster to give aldohexose give
ketohexoses colored pale pink color
condensation
products
95
.-4
it
MALTOSE - consists of 2 glucose units linked u.1.,4, obtained as intermediates in
starch hydrolysis by the amylases. It has a free anomeric carborL and can exist in a and b
forms (can mutarotate), hence it is a reducing sugar.
HOH
n
CELLOBIOSE - has 2 glucose uirits lihked P . 7,4.It is formed by the hydrolysis of
cellulose, can mutarotate and is a reducing sugar. Methylation produces an octamethyl
derivative and subsequent hydrolysis yields tt t" srr"e prodults as those of octamethyl maltose.
SUCROSE - is one glucose + one fructose linked a-1,2.Its sources are sugar cane and
sugar beets. It is NOT a reducing sugar because both reducing groups of the two
monosaccharides are involved in the formation of the glycosidic bond.
HOCFI2
cH2oH
STORAGE I'OLYSACCHARIDES
A. Starch - the storage polysaccharide of higher plants; consists of 2 fractions.
1.) Amylose contains D giucoseunits linked u-11with areducing and non-reducing
end. Molecular weight varies from a few thousand to about 150,000. It gives the
characteristic blue color with iodine due to the ability of the halogen to occupy
a position in the interior of the heiical coil of glucose units when amylose is
suspended in water.
cH2oH CFI.OH
,/\r-O
* 97
t
f
5r.
'3
:i
**,
2.) Amylopectin abranched polysaccharide; short chains (about 30units) of glucose
linked a -L,4 and u-1,6. Molecular weight is 500,000 or higher; gives purple to
red color with iodine.
qH'?oH
7
,r-or
"v).,,
:i CH"OH CH"OH CH" CH"OH CH"OH
&
!i
'tt /-'.', ,1"r, ,1"r, /-r,
(;-L"-(--)"-(1-,).(,-) /-o\
Starch is susceptible to the action of the follgwing hydrolytic enzymes:
c,-amylase found in the digestive tract of animals (saliva and pancreatic juice);
acts on linear portion of amylose chaih'attacking o-1,4 linkages randomly to
yield a mixture of maltose and glucose.
p-amylase found rn plants; attacks from the non-reducing end to yield successive
units of maltose.
when cr- and p- amylase attack amylopectin, a-7,Alinkages near branchpoints
and a-1,6linkages are not hydrolyzed, leaving a highly branched core called
"limit dextrin."
Debranching enzyme or d,-L,6glucosidase hyd.rolyzes bonds at branch points
yielding a mixture of glucose and maltose.
B. Glycogen - structure is similar to amylopectin but more highly branched (branch points
ev_ery 8-10 glucose) and when acted upon by o- *d 0 . amylases give glucose * mhtose
+ "limit dextrin."
STRUCTURAL POLYSACCHARIDES:
A.) Cellulose - consists of D glucose units linked B-1,4. It is found in cell walls of
plants. Strong mineral acids cause partial hydrolysis (Nofe: B-1,4 linkages are
more resistant to hydrolysis) to cellobiose and glucose.
7
99
B. Chondroitin - similar to hyaluronic acid except that the amino srlgar is N-acetyl
D galactosamine. It is also a componextof cell coats. Sulfate esters of chondroitin
at C-4 and C-6 of the amino sugar are major components of. car-tilage tendons,
and bones.
7
C. Peptidoglycans - a combination of polysaccharides with amino acids. The
disaccharide consists of N-acetyl D glucose (NAG) and N-acetylmuramic acid
(NAMA) joined by ap-1,,4 glycosidic bond. Peptidoglycans are found in'bacterial
cell walls which determine many of the physiological characteristics of the
organism they enclose.
Important Esters
ATP ADP
u-D glucose o-D- glucose 6-P
enzyme
H2OjPOCH
cx-D fructose
ATP ADI' g-D fructose 1,5 di P
enzyme H