CARBOHYDRATE

CHEMISTRY
 QUIZ PRETEST

 ¼ sheet of paper
Name ( surname, first name)
Date:
 PRETEST
CARBOHYDRATE CHEMISTRY
 1. Which of the following is NOT a known function of
carbohydrates?

a.structural component of our DNA

b. soften stools and prevents colonic Ca
c. confers our blood type specificity
d. hydrolyzes complex compounds for energy
 PRETEST
CARBOHYDRATE CHEMISTRY

What is the disaccharide form with :

 2.

galactose + glucose?
a. maltose
b. sucrose
c. fructose
d. lactose
 QUIZ 1
CARBOHYDRATES

 3.Which of the
following is the
Fischer projection of
D- Glucose?
 4. Which of the ff statements about human digestion and
absorption of sugars is TRUE?

a. No digestion occurs in the stomach due to high acidity

b. sucrose is broken down to gluc and fruc in the mouth
c. absorption occurs in the large intestines
d. cellulose is broken into numerous glucose units in the
small intestines
 5. The carbon with 4 different atoms
or groups of atoms are attached and
is desribed as asymmetric
a. chiral carbon
b. reducting carbon
c. penultimate carbon
d. enantiomer carbon
 5. This is
a. A-D-glucofuranose
b. B-D-glucofuranose
c. A-D-glucopyranose
d. B-D-glucopranose
7. Storage form of carbohydrate EXCEPT
a. Cellulose
b. starch
c. liver glycogen
d. muscle glycogen
  8 which of the ff is a polysaccharide:

A B C
 LECTURE PROPER
 9. Give the name of this disaccharide

a. α-D-glucofuranosyl-(14) L- glucopyranose
b. B-D-glucofuranosyl-(16) L- glucopyranose
c. α-D-glucopyranosyl-(14) D- glucopyranose
d. B-D-glucopyranosyl-(16) D- glucopyranose
 10. What is the basic formula of all monosaccharides

A. C n(H2O) n
B. CnHnOn
C. C(HO 2)n
D. (CHO) 2n
 OUTLINE OF TOPICS:

 FUNCTIONS OF CARBOHYDRATES
 STRUCTURAL FORMULA
 STRUCTURAL REPRESENTATIONS
 STEREOISOMERS
 CARBOHYDRATES OF PHYSIOLOGIC SIGNIFICANCE
 MONOSACCHARIDES
 DISACCHARIDES
 POLYSACCHARIDES
 DIGESTION AND ABSORPTION OF CARBOHYDRATES
 BIOLOGICAL FUNCTIONS OF
CARBOHYDRATES

 as a storage form of fuel

 1 g CHO = 4 kcal
 chief storage form : starch (plants)
glycogen (animals)
 BIOLOGICAL FUNCTIONS OF
CARBOHYDRATES

 as structural elements
 cellulose ( plant tissues)
 acid mucopolysaccharides &
proteoglycans (animal tissues)
Chitin – in insects and
crustaceans
Peptidoglycan –in bacteria
 BIOLOGICAL FUNCTIONS OF
CARBOHYDRATES

 component of the structural backbone of our DNA

Other FUNCTIONS of CARBOHYDRATES

 Provides adhesions in the cellular membrane

 transport functions – glycoprotein in Ceruloplasmin
(Cu); Transferrin (Fe)
Other FUNCTIONS…
 confer biologic specificity on the surface of animal
cells
Blood typing:
 CARBOHYDRATE
DEFINITION/ CHEMICAL FORMULA

C =O
Carbonyl
group

General Formula is
Cn (H 0) n
2
 CARBOHYDRATE
DEFINITION/ CHEMICAL FORMULA
polyhydroxy aldehydes or ketones or compounds w/c yield these derivatives on
hydrolysis
C =O
Carbonyl
group
 CARBOHYDRATES
STRUCTURAL REPRESENTATION

FISHER
PROJECTION

General Formula

GLUCOSE
C6 H 12 0 6 HAWORTH
PROJECTION

CHAIR
PROJECTION
 CARBOHYDRATES
STRUCTURAL REPRESENTATION

FISHER
PROJECTION

-straight chain representation

-the carbon chain is written vertically

with carbon 1 at the top with the –H
and –OH group to the right and to
the left
 CARBOHYDRATES
STRUCTURAL REPRESENTATION

HAWORTH
PROJECTION

- Carbon 1 is drawn farthest to the right.

The plane of the ring is flat and the –H,-
OH, and CH2OH groups project either
above or below the plane
 CARBOHYDRATES
STRUCTURAL REPRESENTATION

HAWORTH
PROJECTION
-simple flat ring
-only possible for 5 or more carbons,
may assume a 5-member furanose or 6-
member pyranose ring.

5
O O
4 1 4 1

3 2 3 2
 CARBOHYDRATE
STRUCTURAL
REPRESENTATION

FISHER TO HAWORTH
PROJECTION
( RIGHT DOWN RULE)
 CARBOHYDRATE
STRUCTURAL
REPRESENTATION
1. draw either a six or 5-
membered ring including
oxygen as one atom

O O
FISHER TO HAWORTH
PROJECTION

RULES TO DRAWING
2. next number the ring clockwise
starting next to the oxygen

5
O O
4 1 4 1

3 2 3 2
 CARBOHYDRATE
STRUCTURAL
REPRESENTATION 3. If the substituent is to the right
in the Fisher projection, it will be
drawn down in the Haworth
projection
(Down-Right Rule)
FISHER TO HAWORTH
PROJECTION

RULES TO DRAWING
 CA R BO HY DRA T E
ST R U C T URA L RE PR E SE N T A T I O N

4. If the substituent is to the right

in the Fisher projection, it will be
drawn down in the Haworth
FISHER TO HAWORTH projection
PROJECTION (Down-Right Rule)

RULES TO DRAWING
 CARBOHYDRATES
STRUCTURAL REPRESENTATION

-arrangement in space of the

CHAIR
PROJECTION
atoms in a molecule w/c can
be achieved by rotation
about a single bond;

 Chair – relatively rigid

and more stable;
predominates in aqueos
solution of hexoses;

 Boat – seen only on

derivatives with bulky
substituents
 STEREOISOMERS

compounds identical in molecular composition and differ only

in spatial configuration
Types
d/L isomerism
Pyranose and furan ring structure
Alpha and beta isomers
Epimers
enantiomers
VANT HOFFS Rule of “n” (where n is the # of asymmetric
C ):
2 n = no. of possible isomers
EXAMPLES OF STEREOISOMERS
 STEREOISOMERS

 Chiral C – 4 different atoms or groups of atoms are attached;

asymmetric

FORMULA FOR COMPUTING THE NUMBER

OF CHIRAL CARBONS/ SUGAR:

ALDOSE= # OF CARBONS – 2

KETOSE= # OF CARBONS - 3
 EXAMPLE

 How many stereoisomers of

glucose is possible?
 STEREOISOMERS
D/L ISOMERISM

 Dependent on :
 Fisher formula: penultimate
carbon
 D isomer = the –OH in the
penultimate carbon atom(next to
the last ) points to the right
 L isomer points to the left
 STEREOISOMERS
D/L ISOMERISM

 Dependent on :
 Haworth formula:
position of the highest
numbered carbon
carbon 6
 STEREOISOMERISM
PYRANOSE AND FURAN RING

 The stable ring structures

of monosaccharides are
similar to the ring
structures of either pyran
(a six-membered ring) or
furan (a five-membered
ring)
 STEREOISOMERISM
ALPHA AND BETA ISOMERISM

 isomeric forms of
monosaccharides that differ
only in their configuration
about the [anomeric C ]

 DEPENDENT ON : Position ! , the

carbonyl or anomeric carbon
atom

 Mutarotation-“interconversio
n of the α and  anomers in
aqueous solution
 STEREOISOMERISM
ALPHA AND BETA ISOMERISM

 DEPENDENT ON : Position ! , the

carbonyl or anomeric carbon atom

 Alpha isomer: OH grp of the

anomeric C is on :

 Right of fisher projection

 DOWN on the haworth projection

 Beta isoer: OH grp is on the BUDA

 LEFT of fisher projection

 UP on the haworth projection

 STEREOISOMERS
EPIMERS
 stereoisomers that differ only in configuration about one
chiral center with the D-glucose as reference.
 Two major aldohexose in nature, glucose and galactose, are
epimers at carbon 4. Glucose and mannose are C-2 epimers
STEREOISOMERISM
ENANTIOMERS
 CLASSIFICATION OF SUGARS

Monosaccharides (monoses Simplest form, cannot be hydrolyzed anymore to simpler or smaller sugar
or glycoses) ex. Trioses, tetroses, pentoses, hexoses
   
Oligosaccharides Di, tri, tetra, penta, up to 9 or 10
  Most important are the disaccharides
Disaccharides:
(+)-maltose - “malt sugar”, two glucose units (alpha)
(+)-cellobiose -two glucose units (beta)
(+)-lactose - “milk sugar”, galactose & glucose
(+)-sucrose - “table sugar”, glucose & fructose
Polysaccharides or glycans Polymeric sugars. Combination of a long chain of monosaccharides
  joined together by glycosidic bonds ex.
Homopolysaccharides,Heteropolysaccharides,Complex carbohydrates
 
 MONOSACCHARIDES

 simple sugars, most (99%) are straight chain compounds

 contain 3 to 10 C atoms
 names end with “ose”
NAMING OF MONOSACCHARIDES

Number of carbons
as the suffix of the
monosaccharide
NAMING OF MONOSACCHARIDES

FUNCTIONAL group
is placed at the
beginning of the
saccharide
 Aldose OR Ketose
NAMING OF MONOSACCHARIDES

Add
stereoisomerism AS
PREFIX
NAMING OF MONOSACCHARIDES

Putting all the

concepts together
NAMING OF MONOSACCHARIDES

Haworth projection

CARBON 1 OH GROUP
A OR B ISOMERS

CARBON 6 OH GROUP
D/L ISOMERS

Furan or pyran
NAMING OF MONOSACCHARIDES

Haworth projection

CARBON 1 OH GROUP
A OR B ISOMERS

CARBON 6 OH GROUP
D/L ISOMERS

Furan or pyran
 EXAMPLES
NAME THE SUGARS
 MONOSACCHARIDES

 ACCORDING TO whether they are aldose or ketose sugar

MONOSACCHARIDES
MONOSACCHARIDES
KETOSES
MONOSACCHARIDES
KETOSES
 MONOSACCHARIDES AS REDUCING
SUGAR
 Reducing sugars: If the oxygen on the anomeric carbon Of a
sugar is not attached to any other structure,
 A reducing sugar can react with chemical reagents and reduce the
reactive component, with the anomeric carbon becoming oxi­ dized.
 ALL MONOSACCHARIDES are reducing sugars
 MONOSACCHARIDES AS REDUCING
SUGAR

Benedicts Reaction
 5 ml of Benedicts
+ 8 drops of urine
boil for 5 minute
 OLIGOSACCHARIDES

contain 2 to 10 sugar units, linked by “glycosidic bond”

-“disaccharides”- most impt. Physiologically
- those w/ 3 or more units are usually joined to non-sugar
molecules as glycoconjugates
Formation of
NAMING OF DISACCHARIDES
EXAMPLE
DISACCHARIDE

 SUCROSE
 a-D-glucopyranosido-b-D-fructofuranoside/b-D-
fructofuranosido-a-D-glucopyranoside
 Also known as tablet sugar, It is commercially
obtained from sugar cane or sugar beet. Hydrolysis
yield glucose and fructose
 It used pharmaceutically to make syrups, troches
DISACCHARIDES

LACTOSE (milk sugar)

 bD-galactose joined to a-D-glucose via b (1,4) linkage.
 Milk contains the a and b-anomers in a 2:3 ratio.
 b-lactose is sweeter and more soluble than ordinary a-
lactose.
 used in infant formulations, medium for penicillin
production and as a diluents in pharmaceuticals
DISACCHARIDES

 MALTOSE
 2-glucose molecules joined via a(1,4) linkage. Known as malt
sugar, I is produced by the partial hydrolysis of starch (either
salivary amylase or pancreatic amylase). I is used as a
nutrient (malt extract; Hordeum vulgare); as a sweetener and
as a fermentative reagent
DISACCHARIDES

LACTULOSE
 galactose-b-(1,4)-fructose. a semi-synthetic disaccharide (not
naturally occurring)that is not absorbed in the GI tract
 It is used either as a laxative (Chronulac) or in the
management of portal systemic encephalopathy (Cephulac)
 It is metabolized in distal ileum and colon by bacteria to
lactic acid, formic acid and acetic acid (remove ammonia)
DISACCHARIDE AS REDUCING SUGARS
 OLIGOSACCHARIDES

 Trisaccharide: raffinose (glucose, galactose and fructose)

 Tetrasaccharide: stachyose (2 galactoses, glucose and fructose)
 Pentasaccharide: verbascose (3 galactoses, glucose and
fructose)
 Hexasaccharide: ajugose (4 galactoses, glucose and fructose)
 POLYSACCHARIDES

 contain more than 10 sugar units

 maybe linear (cellulose) or branched (glycogen)
 usually polymers (MW from 200,000)
 White and amorphous products (glassy).
 not sweet,not reducing and do not give the typical aldose or
ketose reactions)
 form colloidal solutions
 POLYSACCHARIDES

BIOLOGIC FUNCTION
1. Storage of energy – starch, glycogen inulin, dextrans
2. Structural component – chitin, cellulose
3. Protective – mucopolysaccharides
 POLYSACCHARIDES

 homoglycans (starch,
cellulose, glycogen,
inulin)
 heteroglycans (gums,
mucopolysaccharides)
 or suspensions when
dissolved.
 STARCH

 It is the most common storage polysaccharide in plants

composed of 10 – 30% a-amylose and 70-90% amylopectin
depending on the source.
 The chains are of varying length, having molecular weights
from several thousands to half a million.
 COMPONENTS OF STARCH

1. Amylose – 13- 20% of starch

- linear unbranched chain of
glucose molecules (α 1,4 linkages)

2. Amylopectin – 80 – 85% of starch

- branched chains of glucose
molecules (α 1,4 linkages in the
chain) with branching every 24 –
30 residues via α 1,6 linkages
STARCH
GLYCOGEN (“ANIMAL STARCH”)
 GLYCOGEN STRUCTURE

 Highly branched
 Consists of glucose molecules linked by α 1,4 linkages in
the chain with branching points every 8 to 12 residues
(α 1,6 linkages)
 It is hydrolyzed by both a and b-amylases and by glycogen
phosphorylase
DEXTRIN
 DEXTRIN

 - Glucose residues linked by α 1,6 linkages with additional α

1,2 or α 1,3 bonds
 Products of partial or incomplete hydrolysis of starch
 It is used as plasma extenders (treatment of shock).
 It is also used as molecular sieves to separate proteins and
other large molecules (gel filtration chromatography).
 They are components of dental plaques
CELLULOSE
 CELLULOSE

 Glucose residues joined by β 1,4 linkages

 Major component of vegetable fiber
 Chief constituent of plant cell walls
 Source of bulk in the stool
 CELLULOSE

Products obtained from cellulose

 Microcrystalline cellulose : used as binder-disintegrant in
tablets
 Methylcellulose: suspending agent and bulk laxative
 Oxidized cellulose: hemostat
 Sodium carboxymethyl cellulose: laxative
 Cellulose acetate: rayon; photographic film; plastics
 Cellulose acetate phthalate: enteric coating
 Nitrocellulose: explosives; collodion (pyroxylin)
DIGESTION AND ABSORPTION OF
CARBOHYDRATES
 CARBOHYDRATE DIGESTION AND
ABSORPTION
Major dietary
CHO:starch, sucrose,
and lactose.
Minor fraction:
glycogen, maltose,
glucose and fructose.
Cellulose, pentosans,
inulin, and
oligossacharides are
not digested by non-
ruminants.
 CARBOHYDRATE DIGESTION AND
ABSORPTION

MOUTH:
• Ptyalin or salivary
amylase catalyzes the
hydrolysis of alpha 1, 4
glycosidic linkages
• starch, glycogen and dextrin
 to maltose and
oligosaccharides.
STOMACH:
• no significant hydrolysis
 CARBOHYDRATE DIGESTION AND
ABSORPTION

DUODENUM/ PANCREAS
 pancreatic amylase acts on
partly digested food.
 It is an endoglycosidase also
called α-amylase or
amylopsin .
Alpha-1,4 linkage of starch
 maltose, maltotriose.
Polysaccharide -
disaccharide
 CARBOHYDRATE DIGESTION AND
ABSORPTION
SMALL INTESTINES
 Digestion mediated by enzymes synthesized by cells lining the
small intestine (brush border)
 individual monosaccharides  absorption
 di- and oligosiaccharides  undergo further degradation by luminal
or brush border enzymes of enterocytes

Brush Border Enzymes

Disaccharides Monosaccharides

* Exception is β-1,4 bonds in cellulose

 CARBOHYDRATE DIGESTION AND
ABSORPTION
SMALL INTESTINES
 CARBOHYDRATE DIGESTION AND
ABSORPTION
DIETARY FIBER:
 Fiber or cellulose are not enzymatically digested by
human digestive enzymes.
 Examples of fiber are:
 cellulose, hemicellulose,pectins, gums, mucilages, lignins.
Bacterial flora in the human gut may degrade the more
soluble fibers, releasing the products into the lumen of
the gut
 Fiber functions : Dietary fiber soften stools by virtue
of their hydrating capacity. They also increase bowel
constipation. Prevents colonic CA and diverticuiar
diseases.
 CARBOHYDRATE DIGESTION AND
ABSORPTION
Glucose is transported
through enterocytes
via facilitated
diffusion and majority
by sodium-dependent
facilitated transport.
Glucose enters the
absorptive cells by
binding to transport
proteins, membrane-
spanning proteins
which bind the glucose
molecule on one side
of the membrane and
release it on the
opposite side
 CLINICAL APPLICATION

62 yo male, no What is the diagnosis?

known comorbidities, What is the culprit
complains of sugar?
abdominal bloating, Discuss the
gas and diarrhea biochemical
everytime he drinks explanation of the
ensure or anlene this patient disease and
started 1 month ago. symptoms
He is afebrile, and no What is the basic
episodes of vomiting. treatment of this
condition
 CLINICAL APPLICATION

Diagnosis: Primary Lactose intolerance

CLINICAL APPLICATION

biochemical
explanation of
symptoms:
 Abdominal bloating?
 Gas and flatulence?
 Diarrhea?
 END OF LECTURE

 REMINDER:
 CASE DISCUSSIONS ON MONDAY
 15 MINUTES PER GROUP
 START OF CLASS 1230 NN
 CLINICAL CASES

 15 minute concise discussion

 Focus on the biochemical aspects of the case
 Discuss physiology very briefly
 Simplify concepts
CASE 1

 H.L. 50 yo male, complains of

easy fatigability at work. This
was associated with frequent
urination especially at night. He
was noted to be losing weight
and yet denied loss of appetite.
His father and eldest brother
were both diabetic. His lab
work- up showed elevated
Fasting blood sugar and HBaic.
His urine was glucose +3,
protein 0.
CASE 1

Questions:
 What is the diagnosis and why?
 what is the biochemical
explanation for the patient’s
diagnosis.
 What are the diagnostic tests to
confirm this patients diagnosis
 What is HBaic? How is it
formed? What does it mean?
 What is the biochemical
mechanism for the
complications of the disease?
CASE 2

 M.N. 24 yo female, medical

student, complains of severe
tooth ache. She sought consult
with her dentist. A still shot of
her teeth showed the following.
She does not have regular dental
check- up. She admits to love
eating chocolates and sweets in
between meals.
CASE 2

Guide Questions:
 What is the diagnosis? And why?
 What is the biochemical
explanation for the patient’s
diagnosis.?
 Discuss the biochemical pathway
of the pathology of the disease.
 Discuss the culprit sugar
 Discuss shortly pharmacologic
and non-pharmacologic
treatment of this disease
CASE 3

 J.O. is a 3 month old infant with

history of vomiting post brestfeeding.
She was noted to have distended
abdomenwith cloudy lens. Her pedia
said she is slightly jaundiced with
palpable liver enlargement. She is
being considered to have early
cataract formation.
CASE 3

 Guide questions:
 What is the diagnosis and why?
 What is the culprit sugar?
 Discuss the biochemical explanation
for the patient’s diagnosis.
 What are the diagnostic tests to
confirm this patients diagnosis?
CASE 4

L M , 2 1 y o f e m a le m e d s t u d e nt , so u gh t
c o n su lt f o r h e r we ig h t . sh e sa id sh e h a s b e e n
o b e se sinc e c hild ho o d . S he e x e r c ise 3 x a
we e k o f 1 h r z u m b a e a c h se ssio n, t o o k
o rlist a t f o r se v e ra l m o nt h s, b u t t o no a v a il.
S he is 5 ’ 0 in h e ig ht a nd we ig hs 8 7 k g . H e r
L ip id p ro f ile a nd FB S a r e no r m a l. 2 4 ho u r
fo o d re c a ll is :
 B R E A K FA S T : 2 c u p s w hit e r ic e , 5 sla b s
b a c o n , 2 t e nd e r ju ic y ho t d o g ju m b o
 S N A C K : 1 p int y o u g hu rt lit e
 L U N C H : 1 c u p wh it e ric e , ¼ g r ille d c hic k e n ,
1 c u p c ho p su e y
 S N A C K : 1 c a n c o k e z e ro , 1 d o u b le
c he e sb u rg e r w it h la rg e f rie s
 D I N N E R : 1 b o wl o f wh o le wh e a t o a t s wit h
so y m ilk
 sN A C K : ½ t u b e o f p rin gle s
CASE 4

GUIDE QUESTIONS
 Why is she obese?
 What kind of carbohydrates must
she avoid in her diet
 What kind of carbohydrates must
she retain in her diet
 What are complex and simple
carbohydrates
 Compute her total energy
requirement and design a 24 hr
diet for her
 FIRST SEMESTER TOPICS

 CARBOHYDRATE CHEMISTRY
 CLINICAL CORRELATION ON CARBOHYDRATE chem(4)
 LIPID CHEMISTRY
 CLINICAL CORRELATION ON LIPID CHEM (4)
 AMINO ACID AND PROTEIN CHEMISTRY
 CLINICAL CORRELATION ON PROTEIN CHEM (4)
 ENZYMOLOGY
 CLINICAL CORRELATION ON ENZYMES (2)
 NUCLEIC ACID CHEMISTRY
 MOLECULAR GENETICS AND GENE EXPRESSION(2)
END OF LECTURE
 CLINICAL CORRELATION

 ADDITIONAL READING:
 CASE 1: read on insulin effect on sugar metabolism
 Case 3: Lippincott’s diagram on Galactosemia
 Case 4: Read on types of examples of carbohydrate rich foods , read
on computation of total energy requirment
 QUIZ SECTION A

 Write: SURNAME, FIRST NAME,

 SECTION AND DATE
 Instruction: write True or False
 CASE 1

1. An Hbaic of 9.0 means he has abnormal glucose blood

level for the past 1 months
2. Insulin resistance means there is high blood glucose
due to inability of the glucose to enter cells and be used
3. Demineralization of the tooth comes first than
formation of plaque in the development of tooth decay
4. Use of flouride contining toothpaste addresses the
plaque formation
5. The culprit sugar in tooth decay is fructose
 6. accumulation of galactitol is the cause of early cataract in
the clasical galactosemia
 7. the only reason why there is fasting hypoglycemia in
patient with classical galactosemia is lack of glucose intake
 8. Salmon is a good source of complex complex
carbohydrates.
 9. Complex carbohydrates are starches, wheat, flour, cake
icing.
 10. All monosaccharides requires insulin for entry in all
tissues and cells
END OF CLASS!