Chemistry of Carbohydrates
(polysaccharides)
Dr Gurjinder Singh
Department of Biochemistry,
Polysaccharides
 Consist of repeating units of monosaccharide units or
derivatives ( > 10) held together by glycosidic bond.
 Two types-
A.Homopolysaccharides-
• On hydrolysis single type of monosaccharides. Glucans are
polymers of Glucose & Fructosans are polymers of Fructose.
• B. Heteropolysaccharides-
• On hydrolysis yield a mixture of few monosaccharides or their
derivatives.
Polysaccharides
Homopolysaccharides
• Starch
• Carbohydrate reserve of plants & most important dietary source for man.
• Consist of D-Glucose units held together with α-glycosidic bonds &
known as glucosan or glucans.
• Two polysaccharide components- water soluble amylose(15-20℅) &
water insoluble amylopectin(80-85℅).
• Amylose- unbranched chain with 200-1000 D-Glucose units held by α(1
→ 4) bond.
• Amylopectin- branched chain with both α(1 → 4) & α(1 → 6) bonds.
Acid hydrolysis of starch
• Acid hydrolysis gives following intermediate products:
• Starch Soluble starch amylodextrin Erythrodextrin
acrodextrin Maltose Glucose
• Dietary starch is hydrolyzed by Salivary and pancreatic -amylase.
ꭤ
• These enzymes act on -1,4 glycosidic linkages to give the final
ꭤ
products of dextrins,maltose and isomaltose.
• Dextrins are intermediate products of starch found in honey,
toasted bread and partially hydrolyzed starch.
Dextrin
• Homoglycans ,water soluble food storage forms with both -1,4 and -1,6
ꭤ ꭤ
glycosidic linkages.
• amylodextrin, Erythrodextrin, acrodextrin are starch hydrolyzed products based
on iodine test.
• Amylodextrin , violet color
• Erythrodextrin red color,
• Acrodextrin : no color
• Breakdown products of Starch by enzyme amylase or dilute acids.
• Various intermediates in hydrolysis of Starch(identified by iodine colouration)-
Starch (blue), amylodextrin (violet), erythrodextrin (red) & acrodextrin (no colour).
Dextrans
• Yeast and bacterial polysaccharides produced by
microorganisms.
• Dental plaque of teeth is rich in dextran.
• They are polymers of glucose linked by -1,4 -1,6 and -1,3
ꭤ ꭤ ꭤ
linkages.
• Used as plasma volume expanders due to high molecular
weight.
• Used in transfusions during hypovalemia as it does not easily
go out of vascular compartment .
• Used as Sephadex in chromatography.
.
Homopolysaccharides
• GLYCOGEN-
• Carbohydrate reserve of animals, hence called animal starch.
• Highest conc. in liver followed by muscle & brain.
• Repeating units of Glucose with α(1→4) bond & α(1→6) bond at
branching site.
• Structure similar to amylopectin with more number of branches and
more compact.
Homopolysaccharides
CELLULOSE-
• Occurs extensively in plants & it is totally absent in animals.
• Repeating units of β-D-Glucose linked by β(1,4) bonds.
• Not digested by mammals due to lack of enzyme that cleaves β
glycosidic bond.
• Major constituent of fiber which reduces absorption of Glucose
& cholesterol from intestine also increasing bulk of feces
• Unbranched linear polymer with B-1,4 linkages (300-3000
units)
• Not utilized /digested due to absence of enzyme cellulase
• On partial hydolysis it yields cellobiose similar to maltose
made up of 2 beta subunits linked by B-1,4 linkages
• Processed to produce papers and fibers
Homopolysaccharides
INULIN
• Polymer of Fructose i.e. Fructosan.
• Occurs in dhalia,garlic.onion.
• Used for assessment of GFR.
CHITIN
• N-acetyl D-Glucosamine units held together by
β(1 → 4) glycosidic bonds.
•
• It is tough protective semitransparent substance;
the principal component of arthropods.
• It is found in exoskleton of some
invertebrates. Crabs lobsters and insects.
HETEROPOLYSACCHARIDES OR
MUCOPOLYSACCHARIDES-
• Repeating units of amino sugars & uronic acid.
• More commonly known as Glycosaminoglycans(GAG).
• Ground substance of extracellular matrix is mainly
composed of GAGs.
• MUCOPOLYSACCHARIDES (old name) detected in
mucous membranes.
• Amino sugars are either glucosamine or galactosamine
in their N-acetylated forms.
Hyaluronic acid-
• Consists of repeatd alternate units of β-D-Glucronic acid and N-Acetyl D –
Glucosamine.
• Found in synovial fluid of joints & vitreous humor of eyes.
• Present in connective tissues and gel around ovum.
• Lubricant and shock absorbent in joints.
• Hyaluronidase is the enzyme which breaks this linkage & is present in testes &
seminal fluids.
• All GAG’s except Hyaluronic acid in the body are linked to core proteins, forming
proteoglycans .
• Only GAG that is unsulphated and not attached to protein
• Hyaluronidase is the enzyme plays a role in fertilization.
• It acts on hyaluronic acid present on outer coat of mammalian egg as gel, cleaves
glycosidic bonds of hyaluronic acid, enabling fertilization
Heparin-
• It is a polymer of L-iduronic acid 2 sulphate and N-sulpho -
D glucosamine -6 sulphate linked by β(1 ,4) glycosidic bonds
• Naturally ocouring Anticoagulant; occurs in blood, lung,
liver, kidney.
• Helps in release of lipoprotein lipase clearing lipemic
plasma.
• It prevents intravascular clotting in thromboembolisms.
• Activates antithrobin-III which inhibits conversion of
prothrombin to thrombin
• It is used to treat and prevent deep vein thrombosis and
pulmonary embolisim
Structure of heparin
Chondroitin sulfates
• Composed of β-D-Glucuronic acid and N-Acetyl D
Galactosamine 4 -sulpahte.
• Linked with β(1,3) glycosidic linkage
• Major constituent of bone, cartilage, tendons, heart valves.
• Contributes to the compressibility and weight bearing
capacity of the cartilage.
• Most abundant GAG found in the connective tissue
Dermatan sulfate
• Composed of repeating subunits of β-L-idouronic
acid and N-Acetyl D Galactosamine 4 –sulpahte.
• Mostly occurs in skin & sclera.
• Responsible for maintaining shape of the eyeball.
• Structural role in the matrix of connective tissue,
maintains the shape of tissue
Keratan sulfate
• Composed of D-Galactose and N-
Acetyl glucosamine 6 -sulpahte.
• Occurs in cornea, tendons, cartilage.
• Role in corneal transparency.
Structure of Keratan sulpahte
GAGs Composition Tissue distribution functions
Hyaluronic
acid
β- D glucuronic acid & N-
acetyl D glucosamine
Synovial fluid, joints,
connective tissue,
cartilages, Vitrous
humor of eye
Lubricant, Shock
absorber, helps in
wound healing
Chondroitin- 4
sulphate
β- D glucuronic acid & N-
acetyl D galactosamine-4
sulphate
Cartilage, tendons,
bones & joints, blood
vessel walls
Maintain structure
& shape of
tissue,also as
lubricants in skeletal
tissue
Heparin L-iduronic acid 2 sulphate
and N-sulpho - D
glucosamine -6 sulphate
Blood, lung, liver,
kidney and spleen
Anticoagulant
Dermatan
sulphate
L- iduronic acid & N-
acetyl D galactosamine 4
sulphate
Skin, Blood vessels,
heart valves, cornea
& sclera
Maintain shape of
tissues, eyeball
Keratan
sulphate
β- D Galactose & Nacetyl
D glucosamine 6 sulphate
Cartilage, cornea,
Connective tissues
Role in corneal
transperency
Functions Of GAGs
 Structural component. They are major components
of the extracellular matrix or ground substance.
 Have special ability to bind large amounts of
water, producing a gel like matrix which functions
as a cushion against mechanical shocks
Functions of GAGs
 Negatively charged glycosaminoglycans chain repel each
other, and proteoglycans occupy a very large space and
act as “molecular sieves”, determin­
ing which substances
enter and leave cells.
 They also give elasticity (resilience) to cartilage,
permitting compression and re-expansion.
 They lubricate joints.
Summary
• Define carbohydrates.
• Classify carbohydrates with examples.
• Mention the functions of carbohydrates
• Describe monosaccharides, disaccharides and
polysaccharides as an energy source with examples.
34
Functions of Carbohydrates
1) Energy
• glucose fuels the work of most of the body’s cells
– preferred fuel of NERVOUS TISSUE (the brain, nerves) and
RED BLOOD CELLS (RBC)
• excess glucose is stored as GLYCOGEN in liver and
muscle tissue
35
Functions of Carbohydrates
2) Sparing Body Protein
• if diet does not provide enough glucose, then other
sources of glucose must be found
• if carbohydrate intake < 50 - 100 g, body protein will
be used to make glucose
• an adequate supply of carbohydrate spares body
proteins from being broken down to synthesize
glucose
36
Functions of Carbohydrates
3) Preventing Ketosis (Anti-ketogenic)
• carbohydrates required for the complete
metabolism of fat
• incomplete fat metabolism produces KETONES
• an adequate supply of carbohydrate (> 50 –
100 g per day) prevents KETOSIS
37
Regulation of Blood Glucose
Optimal functioning of the body is dependant on
keeping levels of glucose within certain parameters.
Elevated blood glucose = Hyperglycemia
Low blood glucose = Hypoglycemia
The ENDOCRINE SYSTEM is primarily responsible for
regulating blood glucose. The two main hormones are
INSULIN and GLUCAGON.
38
Regulation of Blood Glucose
39
Diabetes Mellitus
• a disorder of energy metabolism due to failure of insulin to
regulate blood glucose
• results in hyperglycemia
• acute symptoms include thirst, increased urine production,
hunger
• long term consequences include increased risk of heart
disease, kidney disease, blindness, neural damage
• two forms: Type I and Type II
40
Diabetes Mellitus
Type I
• accounts for about 10% of cases
• occurs when b cells of the pancreas are destroyed
– insulin cannot be synthesized
• without insulin, blood glucose levels rise because the
tissues are unable to access the glucose
• death occurs shortly after onset unless given
injections of insulin
41
Diabetes Mellitus
Type II
• occurs when cells of body are unable to respond to
insulin
• called “insulin insensitivity” or “insulin resistance”
• blood glucose levels rise
• insulin secretion increases in an attempt to
compensate
– leads to hyperinsulinemia
42
Hypoglycemia
• dramatic drop in blood glucose
• symptoms similar to an anxiety attack: rapid weak
heart beat, sweating, anxiety, hunger, trembling,
weakness
• RARE in healthy people
• may occur as a result of poorly managed Diabetes or
other causes:
– reactive hypoglycemia
– fasting hypoglycemia
THANK YOU

dr gurjinder polysaccharides and structures.pptx

  • 1.
    Chemistry of Carbohydrates (polysaccharides) DrGurjinder Singh Department of Biochemistry,
  • 2.
    Polysaccharides  Consist ofrepeating units of monosaccharide units or derivatives ( > 10) held together by glycosidic bond.  Two types- A.Homopolysaccharides- • On hydrolysis single type of monosaccharides. Glucans are polymers of Glucose & Fructosans are polymers of Fructose. • B. Heteropolysaccharides- • On hydrolysis yield a mixture of few monosaccharides or their derivatives.
  • 3.
  • 4.
    Homopolysaccharides • Starch • Carbohydratereserve of plants & most important dietary source for man. • Consist of D-Glucose units held together with α-glycosidic bonds & known as glucosan or glucans. • Two polysaccharide components- water soluble amylose(15-20℅) & water insoluble amylopectin(80-85℅). • Amylose- unbranched chain with 200-1000 D-Glucose units held by α(1 → 4) bond. • Amylopectin- branched chain with both α(1 → 4) & α(1 → 6) bonds.
  • 7.
    Acid hydrolysis ofstarch • Acid hydrolysis gives following intermediate products: • Starch Soluble starch amylodextrin Erythrodextrin acrodextrin Maltose Glucose • Dietary starch is hydrolyzed by Salivary and pancreatic -amylase. ꭤ • These enzymes act on -1,4 glycosidic linkages to give the final ꭤ products of dextrins,maltose and isomaltose. • Dextrins are intermediate products of starch found in honey, toasted bread and partially hydrolyzed starch.
  • 8.
    Dextrin • Homoglycans ,watersoluble food storage forms with both -1,4 and -1,6 ꭤ ꭤ glycosidic linkages. • amylodextrin, Erythrodextrin, acrodextrin are starch hydrolyzed products based on iodine test. • Amylodextrin , violet color • Erythrodextrin red color, • Acrodextrin : no color • Breakdown products of Starch by enzyme amylase or dilute acids. • Various intermediates in hydrolysis of Starch(identified by iodine colouration)- Starch (blue), amylodextrin (violet), erythrodextrin (red) & acrodextrin (no colour).
  • 9.
    Dextrans • Yeast andbacterial polysaccharides produced by microorganisms. • Dental plaque of teeth is rich in dextran. • They are polymers of glucose linked by -1,4 -1,6 and -1,3 ꭤ ꭤ ꭤ linkages. • Used as plasma volume expanders due to high molecular weight. • Used in transfusions during hypovalemia as it does not easily go out of vascular compartment . • Used as Sephadex in chromatography.
  • 10.
    . Homopolysaccharides • GLYCOGEN- • Carbohydratereserve of animals, hence called animal starch. • Highest conc. in liver followed by muscle & brain. • Repeating units of Glucose with α(1→4) bond & α(1→6) bond at branching site. • Structure similar to amylopectin with more number of branches and more compact.
  • 12.
    Homopolysaccharides CELLULOSE- • Occurs extensivelyin plants & it is totally absent in animals. • Repeating units of β-D-Glucose linked by β(1,4) bonds. • Not digested by mammals due to lack of enzyme that cleaves β glycosidic bond. • Major constituent of fiber which reduces absorption of Glucose & cholesterol from intestine also increasing bulk of feces
  • 13.
    • Unbranched linearpolymer with B-1,4 linkages (300-3000 units) • Not utilized /digested due to absence of enzyme cellulase • On partial hydolysis it yields cellobiose similar to maltose made up of 2 beta subunits linked by B-1,4 linkages • Processed to produce papers and fibers
  • 14.
    Homopolysaccharides INULIN • Polymer ofFructose i.e. Fructosan. • Occurs in dhalia,garlic.onion. • Used for assessment of GFR.
  • 16.
    CHITIN • N-acetyl D-Glucosamineunits held together by β(1 → 4) glycosidic bonds. • • It is tough protective semitransparent substance; the principal component of arthropods. • It is found in exoskleton of some invertebrates. Crabs lobsters and insects.
  • 18.
    HETEROPOLYSACCHARIDES OR MUCOPOLYSACCHARIDES- • Repeatingunits of amino sugars & uronic acid. • More commonly known as Glycosaminoglycans(GAG). • Ground substance of extracellular matrix is mainly composed of GAGs. • MUCOPOLYSACCHARIDES (old name) detected in mucous membranes. • Amino sugars are either glucosamine or galactosamine in their N-acetylated forms.
  • 19.
    Hyaluronic acid- • Consistsof repeatd alternate units of β-D-Glucronic acid and N-Acetyl D – Glucosamine. • Found in synovial fluid of joints & vitreous humor of eyes. • Present in connective tissues and gel around ovum. • Lubricant and shock absorbent in joints. • Hyaluronidase is the enzyme which breaks this linkage & is present in testes & seminal fluids. • All GAG’s except Hyaluronic acid in the body are linked to core proteins, forming proteoglycans . • Only GAG that is unsulphated and not attached to protein • Hyaluronidase is the enzyme plays a role in fertilization. • It acts on hyaluronic acid present on outer coat of mammalian egg as gel, cleaves glycosidic bonds of hyaluronic acid, enabling fertilization
  • 21.
    Heparin- • It isa polymer of L-iduronic acid 2 sulphate and N-sulpho - D glucosamine -6 sulphate linked by β(1 ,4) glycosidic bonds • Naturally ocouring Anticoagulant; occurs in blood, lung, liver, kidney. • Helps in release of lipoprotein lipase clearing lipemic plasma. • It prevents intravascular clotting in thromboembolisms. • Activates antithrobin-III which inhibits conversion of prothrombin to thrombin • It is used to treat and prevent deep vein thrombosis and pulmonary embolisim
  • 22.
  • 23.
    Chondroitin sulfates • Composedof β-D-Glucuronic acid and N-Acetyl D Galactosamine 4 -sulpahte. • Linked with β(1,3) glycosidic linkage • Major constituent of bone, cartilage, tendons, heart valves. • Contributes to the compressibility and weight bearing capacity of the cartilage. • Most abundant GAG found in the connective tissue
  • 25.
    Dermatan sulfate • Composedof repeating subunits of β-L-idouronic acid and N-Acetyl D Galactosamine 4 –sulpahte. • Mostly occurs in skin & sclera. • Responsible for maintaining shape of the eyeball. • Structural role in the matrix of connective tissue, maintains the shape of tissue
  • 27.
    Keratan sulfate • Composedof D-Galactose and N- Acetyl glucosamine 6 -sulpahte. • Occurs in cornea, tendons, cartilage. • Role in corneal transparency.
  • 28.
  • 29.
    GAGs Composition Tissuedistribution functions Hyaluronic acid β- D glucuronic acid & N- acetyl D glucosamine Synovial fluid, joints, connective tissue, cartilages, Vitrous humor of eye Lubricant, Shock absorber, helps in wound healing Chondroitin- 4 sulphate β- D glucuronic acid & N- acetyl D galactosamine-4 sulphate Cartilage, tendons, bones & joints, blood vessel walls Maintain structure & shape of tissue,also as lubricants in skeletal tissue Heparin L-iduronic acid 2 sulphate and N-sulpho - D glucosamine -6 sulphate Blood, lung, liver, kidney and spleen Anticoagulant Dermatan sulphate L- iduronic acid & N- acetyl D galactosamine 4 sulphate Skin, Blood vessels, heart valves, cornea & sclera Maintain shape of tissues, eyeball Keratan sulphate β- D Galactose & Nacetyl D glucosamine 6 sulphate Cartilage, cornea, Connective tissues Role in corneal transperency
  • 31.
    Functions Of GAGs Structural component. They are major components of the extracellular matrix or ground substance.  Have special ability to bind large amounts of water, producing a gel like matrix which functions as a cushion against mechanical shocks
  • 32.
    Functions of GAGs Negatively charged glycosaminoglycans chain repel each other, and proteoglycans occupy a very large space and act as “molecular sieves”, determin­ ing which substances enter and leave cells.  They also give elasticity (resilience) to cartilage, permitting compression and re-expansion.  They lubricate joints.
  • 33.
    Summary • Define carbohydrates. •Classify carbohydrates with examples. • Mention the functions of carbohydrates • Describe monosaccharides, disaccharides and polysaccharides as an energy source with examples.
  • 34.
    34 Functions of Carbohydrates 1)Energy • glucose fuels the work of most of the body’s cells – preferred fuel of NERVOUS TISSUE (the brain, nerves) and RED BLOOD CELLS (RBC) • excess glucose is stored as GLYCOGEN in liver and muscle tissue
  • 35.
    35 Functions of Carbohydrates 2)Sparing Body Protein • if diet does not provide enough glucose, then other sources of glucose must be found • if carbohydrate intake < 50 - 100 g, body protein will be used to make glucose • an adequate supply of carbohydrate spares body proteins from being broken down to synthesize glucose
  • 36.
    36 Functions of Carbohydrates 3)Preventing Ketosis (Anti-ketogenic) • carbohydrates required for the complete metabolism of fat • incomplete fat metabolism produces KETONES • an adequate supply of carbohydrate (> 50 – 100 g per day) prevents KETOSIS
  • 37.
    37 Regulation of BloodGlucose Optimal functioning of the body is dependant on keeping levels of glucose within certain parameters. Elevated blood glucose = Hyperglycemia Low blood glucose = Hypoglycemia The ENDOCRINE SYSTEM is primarily responsible for regulating blood glucose. The two main hormones are INSULIN and GLUCAGON.
  • 38.
  • 39.
    39 Diabetes Mellitus • adisorder of energy metabolism due to failure of insulin to regulate blood glucose • results in hyperglycemia • acute symptoms include thirst, increased urine production, hunger • long term consequences include increased risk of heart disease, kidney disease, blindness, neural damage • two forms: Type I and Type II
  • 40.
    40 Diabetes Mellitus Type I •accounts for about 10% of cases • occurs when b cells of the pancreas are destroyed – insulin cannot be synthesized • without insulin, blood glucose levels rise because the tissues are unable to access the glucose • death occurs shortly after onset unless given injections of insulin
  • 41.
    41 Diabetes Mellitus Type II •occurs when cells of body are unable to respond to insulin • called “insulin insensitivity” or “insulin resistance” • blood glucose levels rise • insulin secretion increases in an attempt to compensate – leads to hyperinsulinemia
  • 42.
    42 Hypoglycemia • dramatic dropin blood glucose • symptoms similar to an anxiety attack: rapid weak heart beat, sweating, anxiety, hunger, trembling, weakness • RARE in healthy people • may occur as a result of poorly managed Diabetes or other causes: – reactive hypoglycemia – fasting hypoglycemia
  • 43.