Carbohydrates of Physiological Significance 1
CARBOHYDRATES OF PHYSIOLOGICAL
SIGNIFICANCE
Carbohydrates
- Widely distributed in plants and animals
- Have important structural and metabolic roles
- Plants: synthesize glucose from carbon dioxide and water by
photosynthesis and stored as starch or used to syntheszie
the cellulose of the plant cell walls
- Animals : can synthesize glucose by from amino acids
Glucose
- Most important carbohydrate
- Dietary carbs are absorbed into the bloodstream as glucose
formed by hydrolysis of dietary starch and disaccharides and
other sugars are converted to glucose in the liver
- Major metabolic fuel of humans, universal fuel of the fetus
- Precursor for synthesis of all other carbohydrates in the body
including
 glycogen: storage
 ribose and deoxyribose: nucleic acids
 galactose: synthesis of lactose in milk
 glycolipids and glycoproteins
Diseases associated with carbohydrate metabolism
- fiber, cellulose from plant cell walls (glucose polymer) and
Diabetes mellitus
- Galactosemia
- Glycogen storage diseases
- Lactose intolerance
Glycobiology
- study the roles of sugars in health and disease
Glycome
- 3. Haworth projection - viewed from the side and above the
entire complement of sugars of an organism whether free or
in complex molecules
Glycomics
- analogous term to genomics and proteomics
- Comprehensive study of glycomes including genetic,
physiological, pathologial and other aspects
Oligosaccharides
- encode biological information that depends on their
constituent sugars, sequences, and linkages
CLASSIFICATION OF CARBOHYDRATES
1. Monosaccharides
- cannot be hydrolyzed into simpler carbohydrates
- trioses, tetroses, pentoses, hexoses, or heptoses
(depending on number of C atoms)
- aldoses or ketoses (depending on whether they have an
aldehyde or ketone group)
- polyols (sugar alcohols, from reduced aldehydes or
ketones; synthesized by the reduction of monosaccharides
for use in the manufacture of foods for weight reduction
for diabetes (poorly absorbed and yield only half the energy
of sugars)
2. Disaccharides
- condensation products of two monosaccharide units
- Lactose, maltose, isomaltose, sucrose and trehalose
3. Oligosaccharides
- 3-10 monosaccharides
- Most digested by human enzymes
4. Polysaccharides
- >10 monosaccharide units
- Starches or dextrins
- Maybe linear or branched polymers
- Sometimes classified as hexosans or pentosans, deoending in
the constituent monosaccharides (hexoses or pentoses)
- Nonstarch polysaccharides in food are not digested by
human enzymes and are the major component of dietary
inulin , the storage carbohydrate in some plants (fructose
polymer)
BIOMEDICALLY, GLUCOSE IS THE MOST IMPORTANT
MONOSACCHARIDE
The Structure of Glucose Can Be Represented in Three Ways
1. Straight chain
2. Cyclic formation
plane of the ring, the bonds nearest to the viewer are bold
and thickened
Hemiacetal
- a cyclic structure formed by reaction between the aldehyde
group and a hydroxyl group
- Thermodynamically favored and accounts for other
properties
Isomerism (Glucose has 4 asymmetric carbon atoms)
1. D and L isomers
- determined by the spatial relationship to the parent
compound, glycerose (three-carbon glyceraldehyde)
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- Orientation of the -H and -OH groups around the carbon
atom adjacent to the terminal alcohol carbon determines
whether the sugar belongs to the D or L series (-OH right = D
isomer)
- most of the naturally occuring monosaccharides are D sugars
and the enzymes responsible for their metabolism are
specific for this configuration
2. Optical activity due to the presence of asymmetric carbon
- when a beam of plane-polarized light is passed through a
solution of an optical isomer, it rotates to either the right =
dextrorotatory or left = levorotatory
- independent of the stereochemistry
- glucose is dextrorotatory in solution = dextrose
3. Pyranose and furanose ring structures
- glucose in solution is 99% in pyranose form
- similar to the ring structures of either pyran (6-membered
ring) or furan (five-membered ring)
4. Alpha and beta anomers
- ring structure of an aldose is a hemiacetal since it is formed
by reaction between an aldehyde and an alcohol group;
ketose is a hemiketal
- Crystalline glucose is α-D-glucopyranose
- The cyclic structure is retained in the solution but isomerism
occurs about position 1, the carbonyl or anomeric carbon
atom, to give a mixture of α-glucopyranose (38%) and β-
glucopyranose (62%)
- steroids as the aglycone
Less than 0.3% is represented by α- and β- anomers
5. Epimers
- Isomers differing as a result of variations in configuration of
the -OH and -H on carbon atoms 2, 3, and 4
- Mannose (Carbon 2), Galactose (Carbon 4)
6. Aldose-Ketose Isomerism
- Same formula but potential aldehyde/keto group
- Aldoses: reducing compounds/sugars; basis for simple
chemical test for glucose in urine in poorly controlled
diabetes mellitus
MANY MONOSACCHARIDES ARE PHYSIOLOGICALLY IMPORTANT
Metabolic intermediates in glycolysis
- derivatives of trioses, tetroses and pentoses, sedoheptulose
Pentoses
- important in nucleotides, nucleic acids, and several
coenzymes
Physiologically most important hexoses:
Carbohydrates of Physiological Significance 2
1. Glucose
2. Galactose
3. Fructose
4. Mannose
Important carboxylic derivatives of glucose
1. D-glucoronate: glucoronide formation and in
glycosaminoglycans
2. L-iduronate: glycosaminoglycans
3. L-gulonate: intermediate in the uronic acid pathway
SUGARS FORM GLYCOSIDES WITH EACH OTHER COMPOUNDS
AND WITH EACH OTHER
Glycosides
- formed by condensation between the hydroxyl group of the
anomeric carbon of a monosaccharide and a second
compound that may be another monosaccharide or a
glycone
- If the second group is also a hydroxyl, the O-glycosidic bond
is an acetal link because it results from a reaction between a
hemiacetal group (formed from an aldehyde and an -OH
group) and another -OH group
• If the hemiacetal portion is glucose → glucosde
• If galactose → galactoside
- If the second group is an amine, an N-glycosidic bond is
formed (adenine and ribose in nucleotides)
- widely distributed in nature; aglycone may be methanol,
glycerol, sterol, phenol, or base such as adenine
- Those important to the heart, cardiac glycosides, all contain
• Ouabain: derivatives of digitalis and strophantus;
inhibitor of the Na-K-ATPase of the cell membranes
- Streptomycin: antibiotic
Deoxy Sugars Lack an Oxygen Atom
- one hydroxyl group has been replaced by hydrogen
- Example. Deoxyribose (The deoxy sugar L-fucose occurs in
glycoproteins; 2-deoxyglucose is used experimentally as an
inhibitor of glucose metabolism
Amino Sugars (Hexosamines) Are Components of Glycoproteins,
Gangliosides, and Glycosaminoglycans
1. D-glucosamine - constituent of hyaluronic acid
2. D-galactosamine/ Chrondrosamine - constituent of
chondroitin
3. D-mannosamine
- Several antibiotics, eg. Erythromycin, contain amino sugars
which are important for their antibiotic activity
Maltose, Sucrose, Lactose and Important Disaccharides
- sugars composed of two monosaccharide residues linked by
a glycoside bonds
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- Hydrolysis of sucrose → glucose + fructose or “invert sugar”
(fructose is strongly levorotatory and changes the weaker
dextrorotatory action of sucrose
POLYSACCHARIDES SERVE STORAGE AND STRUCTURAL
FUNCTIONS
Physiologically important carbohydrates
1. Starch
- homopolymer of glucose forming an α -glucosidic chain
(glucosan or glucan)
- Most important dietary carbohydrate in cereals, potatoes,
legumes and other vegetables
- Two main components:
• Amylose (13-20%) - which has a nonbranching helical
structure
• Amylopectin (80-87%) - branched chains, 24-30 glucose
residues with α 1→4 linkages in the chains and by α 1→6
linkages at the branch points
- extent to which it is hydrolyzed by amylase is determined by:
• Structure
• Degree of crystallization or hydration (the result of
cooking)
• Whether it is enclosed in intact (and indigestible) plant
cell walls
Glycemic index
- measure of its digestibility, based on the extent to which it
raises the blood concentration of glucose compared with an
equivalent amount of glucose or a reference food such as
white bread or boiled rice
- 1 or 100% = starched readily hydrolyzed in the small intestine
- 0 = those that are not hydrolyzed at all
2. Glycogen
- storage polysaccharide in animals
- Animal starch
- A more highly branched structure than amylopectin
- 12-15 α -D-glucopyranose residues (α 1→4 linkages) with
branching by means of α 1→6 glucosidic bonds
- Muscle glycogen granules are spherical and contain up to
60,000 glucose residues (β -particles)
- There are similar granules and also rosette of glycogen
granules that appear to be aggregated b-particles
3. Inulin
- -
polysaccharides of fructose (a fructosan) found in tubers and
roots of dahlias, artichokes, and dandelions
- -
Readily soluble in water and used to determine glomerular
filtration rate
Carbohydrates of Physiological Significance 3
- Not hydrolyzed by intestinal enzymes, so has no nutritional
value
4. Dextrins
- intermediates of the hydrolysis of starch
5. Cellulose
- chief constituent of the plant cell walls
- Insoluble and consists of β -D-glucopyranose units linked by
β 1→4 bonds to form long, straight chains strengthened by
cross-linking hydrogen bonds (mammals lack enzyme to
hydrolyze β 1→4 bonds and cannot digest cellulose)
- Major component of dietary fiber
- Used as a major energy source of microorganisms, ruminant
and other herbivores that can hydrolyze the linkages and
ferment the products; there is some bacterial metabolism in
the color by bacteria
6. Chitin
- structural polysaccharide in the exoskeleton of crustaceans
and insects and also in mushrooms
- Consists of N-acetyl-D-glucosamine units joined by β 1→4
glycosidic bonds
7. Pectin
- occurs in fruits
- Polymer of galacturonic acid linked α 1→4, with some
galactose and/or arabinose branches and is partially
methylated
8. Glycosaminoglycans
- mucopolysaccharides
- Complex carbohydrates containing amino sugars and uronic
acids
- May be attached to a protein molecule to form a
proteoglycan
• Provide the ground or packing substance of connective
tissue
• Hold large quantities of water and occupy space
• Cushion or lubricate other structures
• Large number of -OH groups and negative charges on the
molecule, which by repulsion, keep the carbohydrate
chains apart
• Hyaluronic acid, chondroitin sulfate, heparin
9. Glycoproteins (mucoproteins)
Proteins + branched or unbranched oligosaccharide chains
including fucose
Occur in cell membranes and many proteins are glycosylated
Dannielle Divine Lagradilla Tirado 2019
 Carbohydrates of Physiological Significance 4

- Sialic acids (constituents of glycoproteins and gangliosides)

are N- or O-acyl derivatives of neuraminic acid
• Nine-carbon sugar derived from mannosamine (epimer of
glucosamine) and pyruvate

CARBOHYDRATES OCCUR IN CELL MEMBRANES AND IN

LIPOPROTEINS
- 5% of the weight of cell membranes is the carbohydrate part
of glycoproteins and glycolipids
- Presence on the outer surface of the plasma membrane, the
glycocalyx, has been shown with the use of plant lectins (bind
specific glycosyl residues)
• Concanavalin A: binds α-glucosyl and α-mannosyl
- also present in apoprotein B or plasma lipoproteins

Glycophorin
- major integral membrane glycoprotein of human
erythrocytes
- Has 130 amino acid residues
- Spans the lipid membrane with polypeptide regions outside
both the external and internal (cytoplasmic) surfaces
- Carbohydrate chains are attached to the amino terminal
portion outside the external surface

Dannielle Divine Lagradilla Tirado 2019