CHAPTER IX

CARBOHYIIRATES

Carbohydrates are polyhydroxycnrbonyl compounds (nldehydes or ketones) or substances that

yield these compounds ttpon hydrolysis. The chapter incltLdes isomirism, which is the abilie of two or
more compounds with the same contposition (same ru.Lmber ondkind of atoms) bg1 different constittttion
(different lnanner of nttacltment of atoms). lt also includes the
functions, clnssificatiin of carbohydrntes,
the structure of glucose, chemical react[ons, and linkages in the
formation of d.iiaccharides and
polysaccharides.

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

2. Position isomers, e.g., 1-chloropropane and 2-chloropropane

cH3-cH2-CH2CI CH3-CH2-CH'
I

CI

3. Functional isomers, e.g., ethyl alcohol and dimethyl ether

cH3-cH2-OH CHr-O-CH3

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

Fumaric acid (trans) maleic acid (cis)

MP = 302"C MP = 130'C
Insoluble in water soluble in water

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
\

H_C_OH [ul ,'o = +13'5"

Cr lL: 1

cH20H

b.DiastereomersarenotmirrorimagesofeachoF"''Theyhavedifferent
MR BP and solubiiities, e'g' erythrose

H-C=O H-C=O H-C=O

H_C: O
ll
H_C-OH HO_C_H
1t
I l

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

CrHu C,H, C,H, C,H,

I II IIi ry

I and II are enantiomers, III and IV are enantiomers, IV is the diastereomer of

I and TI.
The number of isomeric forms = 2" where n is the number of chiral carbons,
. e.9., trt the case of 2,3 dichloropentane, there are two chiral carbons, hence
there will be four isomeric forms.
RACEMIC MIXTURES - are equimolar amounts of dextrorotatory and levorotatory
isomers, anci therefore do not exhibit optical activity. On the other hand, 2,3, dichlorobutane
has two chiral centers but do not exhibit optical activity. These are called MESO compounds
( nrolecules with chiral centers which are not optically active) due to the presence of planes
of symmetry,

CH, CH, CH, CH,

u --f-cr o-f H ci-*]_-u u*J- cr
cr-f- H
l

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:

CHO CHO CHO CH^OH

I
ll
E
H-C-OH
1

HO-C-H
I

H-C-OH
I t'
C:O
i I i l
HO-q-H
I

HO_C-H HO-C-H HO_C-H

I I

H-C-OH
I I

H-C_OH HO-C-H H_C-OH

I

H-C-OH
I I

H-C_OH
I

H-C_OH H-C-OH
I L
I

cH,oH cH2oH cH2oI{ cH2oH

D(+) glucose D(+)mannose D(+) galactose D(-) fructose

All 4 sugars are D- sugars because they have the same configuration as D-
glyceraldehyde on the penultimate carbory C-5.

2. D- fructose is a keto hexose and is a structural isomer of the other 3.

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.

5. D(+) glucose and D(+) mannose are epimers at C-2.

6. D(+) glucose and D(+) galactose are epimers at C-4.

89
Apparently, a special type of diastereomerism exists in

a. epimers - diastereomers that differ in a single carbon atom, and

b. anomers - diastereomers that differ in a atom, and the single atom is

carbon-1.

a.) Skeletal or structural functionsl e ,g.r cellulose, the major structural component
of plant cell walls; and peptidoglycans of bacterial cell walls.

b.) Storage, nuttient and reservoir of chemical energy, to be enlarged or depleted

as the organism needs eg., glycogen and starch, which.are produied or
consumed in line with the energy needs of the cell.

According to the number of sugar units

a.) Monosscchtffides are simple sugars that could not be hydrolyzed further
into smaller units under reasonably mild conditions. They are generally
crystalline compounds which are soluble in water and has a sweet taste,
e.g., glucose.
b.) oligosaccharides are hydrolyzable polymers of monosaccharides
containing 2-6 molecules of simple sugar, e.g., sucrose.
c.) Polysaccharides are very long chains or polymers of monosaccharides
which may be linear or branched in structure; usually tasteless and water
insoluble.
c'1. Homopolysaccharides are made up of only one kind of
monosaccharide, e.g., starch and glycogen.
c.2. Heteropolysaccharides are made up of 2 or more different kinds of
monosaccharides, e.g., hyaluronic acid.

According to functional groups

a.) Aldoses contain the aldehyde group, e.g., glucose, mannose, galactose.
b.) Ketoses contain the ketone group e.g., fructose.

9+.] 3 :,CNEI,tiSTRY fOr NURSING STUDENTS

 J. According to the number of carbon atoms
a.) Triose contains 3 carbon atoms, e.g., glyceraldehyde.
#
tr b.) Tetrose contains 4 carbon atoms, e.9., erythrose.
ffi
ffi' c.) Pentose contains 5 carbon atoms/ e.g., ribose"
7 d.) Hexose contains 6 carbon atoms, e.g., glucose.
ffi

$
$,
,&
$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

R-CH-OR' (hemiacetal formation)

I

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

Anomeric OH is on the same side Anomeric OH is trans to the OH of

as OH of C-5, the reference carbon. the reference carbon.

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.

Less stable form More stable form

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

u-D(+) glucose open form of P-D (*) glucose

(36%) D-glucose (1%) (67%)

The structure of glucose may be shown using

a. Puckered chair and boat forms:

r CH"OH

cH,oH

92 BIOCHE['IISTRY fOT NURSiNG STUDENTS

b. Fischer projection formulas

H- ,oH H -c,I' oH i I H-C-OH

It
H- toH O H-C-OH
I

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

cx - D-Clucose cx - D-Gluco- cx - D-Calacto B - L-Arabino #

pyranose furanose furanose Pyranose

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)

4. They form glycosides.

cH3oH' HCl
methyl B-D glucopyranoside

CHrl or
glucose penta- O -methyl 2, 3, 4,6 tetraO- -
(cH)2so4
B-D glucose --.r- methyl D-glucose

Ano tlter m o no s ac char i de

Disacchalide

5. Monosaccharides give characteristic color reactions ih several qualitative tests.

This reaction is the basis for the Molisch test for carbohydrates.

HocFr, (cFroH) 3cFro {#:* qL cHo

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

6. Based on their ability to reduce other substances, monosaccharides give the

following results:

Tests Reagents & Product Positive result

procedures responsible
for color
Benedict's test CuSOn, NarCO, Cu,Ol
sodium citrate
-+ Brick red
precipitate
Fehling's test CuSO*, sodium CurOl Brick red
tartrate + precipitate
Barfoed's tesf Cu (Ac). in dilute HCl,
can distu.rguish between
-t
Cu,Ol Brick red
precipitate
reducing mono- and
disaccharides
Tollen's test AgNO, I\JH, Ag mirror Deposition of
Ag mirror
Phenylhydraztrre Phenylhydrazine + phenylosa- Ye1low
test heat zone precipitate

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.

ISOMALTOSE-has 2 glucose units linked a-1., 6. Methylation gives an octamethyl

derivative which hydrolyzes to 2,3,4,6 tetra-O-methyl D glucose and2,3,4 tri-O-methyl D
glucose.
(
\
S

96 BlocHEMrsT.Ry for rluRSrNG sruDENTS

 LACTOSE - has one glucose and one galactose unit linked P-1,4. It is the disaccharide
in mi1k. It can mutarotate and is reducing.

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."

NUTRIENT POLYSACCHARIDES - e.g. inulin, found in bulbs of many plants, consists of

fructofuranose units joined together by b-2,1. glycosidic lirkage.

98 BIOCHEMISTRY fOT NURSING STUDENTS

 u-

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

B.) Pectins - contain arabinose, galactose and galacturonic acid.

C.) Hemicelluloses - are not cellulose derivatives; a homopolymer of D-xylose linked

p-7,4.

D.) Chitin a homopolymer of N-acetyl D glucosamine; found

- in the shell of
crustaceans and scales of insects.
);
3 OTHER HETEROPOLYSACCHARIDES

CeIl coats of animal cells contain giycolipids, glycoproteins, and mucopolysaccharides

(gelatinous subStances of high MW, up to 5 x 10 6 ) which serve both as lubricant and as
sticky cement.
:
1 A. Hyaturonic acid is a heteropolysaccharide composed of alternating units of D-
glucuronic acid and N-acetyl - O- glucosamine with a p-1,3 linking'the two
monosaccharides, which in turn is linked B-1,4 to the next repeating unit.
Hyaluronic acid is found in the vitreous humor of the eye and in the umbilical
cord, and is water solubie, forming viscous solutions.

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

1 OO BIOCHEMISTRY fOT NURSING STUDENTS