VIETNAMATIONAL UNIVERSITY HCMC
INTERNATIONAL UNIVERSITY
BTBC209IU
Biochemistry 1
Nguyen Kim Truc (PhD)
Office: A1.705
Email: nktruc@[Link]
AY 2019-2020, semester 2
Carbohydrates (cont)
Monosaccharides derivative forms
• A variety of chemical and enzymatic reactions produce
derivatives of the simple sugars
• Some of the most common are:
Sugar acids
Sugar alcohols
Deoxy sugars
Sugar esters
Amino sugars
Acetals, ketals, and glycosides
Monosaccharides derivative forms
Reducing sugars are sugars with free anomeric carbons - they will
reduce oxidizing agents, such as peroxide, ferricyanide and some
metals (Cu2+ and Ag+).
These redox reactions oxidize the sugar to a sugar acid.
Glucose is a reducing sugar - so these reactions are the basis for
diagnostic tests for blood sugar
Monosaccharides derivative forms
aldonic acids exist in
equilibrium with their
lactone forms
Oxidation of
glucose to form
sugar acids
Monosaccharides derivative forms
• Sugar alcohols: are formed by mild reduction of sugars
• Deoxy sugars: constituents of DNA, etc.
• Sugar esters: phosphate esters like ATP are important
• Amino sugars contain an amino group in place of a hydroxyl
group
• Acetals, ketals and glycosides: basis for oligo- and
polysaccharides
Sugar alcohols
Sugar alcohols
Sugar alcohols are sweeteners
Sugar alcohols such as sorbitol, mannitol, and
xylitol sweeten many “sugarless” gums and
candies
Why sugar alcohols are used as sweetener in
diabetics food?
Deoxy sugars
• Deoxy sugars are monosaccharides with one or more hydroxyl
groups replaced by hydrogens
• 2-Deoxy-D-ribose is a constituent of DNA
Deoxy sugars
• Deoxy sugars are monosaccharides with one or more hydroxyl
groups replaced by hydrogens
• 2-Deoxy-D-ribose is a constituent of DNA
• Rhamnose is a component of ouabain, a toxic “cardiac glycoside”
Deoxy sugars
• Deoxy sugars are monosaccharides with one or more hydroxyl
groups replaced by hydrogens
• 2-Deoxy-D-ribose is a constituent of DNA
• Rhamnose is a component of ouabain, a toxic “cardiac glycoside”
• Fucose is a component of some cell walls
Sugar esters
• Phosphate esters of glucose, fructose, and other
monosaccharides are important metabolic intermediates
• The ribose moiety of nucleotides such as ATP and GTP is
phosphorylated at the 5’-position.
Several sugar esters important in metabolism.
Amino sugars
• Sugars with an amino group at C-2 are amino sugars
• They are found in many oligosaccharides and polysaccharides
Amino sugars
a supplement to support the structure and function of joints, and
the marketing is targeted to people suffering from osteoarthritis
Oligosaccharides
• Disaccharides are the simplest oligosaccharides
• Two monosaccharides linked by a glycosidic bond
• Each unit in an oligosaccharide is termed a residue
• Each of these (except for sucrose) possesses one free
unsubstituted anomeric carbon, and is thus a reducing sugar
• Sucrose is not a reducing sugar – it does not have a free
anomeric carbon
Disaccharides
The structures of several important disaccharides. Note the
configurations at the anomeric carbons. Note also that sucrose is
not a reducing sugar.
Trehalose – A natural protectant for bugs
Insects use an open circulatory system to circulate “hemolymph”
(insect blood). The “blood sugar” is trehalose, an unusual,
nonreducing disaccharide. Trehalose may act as a natural
cryoprotectant, protecting the insect from damage due to
freezing temperatures.
Macrolides
Macrolides (macrocyclic lactone ring
to which one or more deoxy sugar
maybe attached). The lactone rings
are usually 14-, 15-, or 16-
membered) belong to the
polyketide class of natural products.
Some macrolides have antibiotic or
antifungal activity and are used as
pharmaceutical drugs.
Macrolides
Erythromycin is an antibiotic produced by
a strain of Streptomyces erythreus
Treatment: respiratory tract
infections, skin infections,
chlamydia infections, pelvic
inflammatory disease, and syphilis
Macrolides
Clarithromycin Roxithromycin
Treatment: pneumonia, skin Treatment: respiratory tract,
infections, H. pylori infection, urinary and soft tissue infections
Lyme disease
A Variety of Higher Oligosaccharides
Occur in Nature
• Oligosaccharides occur
widely as components of
antibiotics (derived from
various sources).
• Streptomycin is an
oligosaccharide produced
by Stretomyces griseus.
Alpha-Gal and red meat allergy
galactose-α-1,3-galactose
Alpha-gal and red meat allergy
• Many people in the southern United
States have become allergic to red
meat in recent years
• The cause is bites from certain ticks,
particularly the lone star tick
• These tick bites trigger an immune
response against the disaccharide
galactose-α-1,3-galactose, known
colloquially as “alpha-gal”
Alpha-gal and red meat allergy
• Most mammals (but not humans) synthesize alpha-gal
• Ticks that feed on deer and other mammals can introduce
alpha-gal into the human blood stream via tick bites
• Because alpha-gal is foreign to humans, it is antigenic, and the
human immune system produces anti-alpha-gal
immunoglobulin E (IgE) antibodies
• Once bitten, persons who eat red meat (beef, pork, lamb) may
experience a severe reaction, including swelling, hives, and
anaphylaxis within a few hours
Alpha-gal and red meat allergy
Polysaccharides
Functions: storage, structure, recognition
• Nomenclature for polysaccharides is based on their
composition and structure
• Homopolysaccharide – a polysaccharide that contains only one
kind of monosaccharide
• Heteropolysaccharide – a polysaccharide made of several
monosaccharides
• Starch and glycogen are storage molecules
• Chitin and cellulose are structural molecules
• Cell surface polysaccharides are recognition molecules
Starch
A plant storage polysaccharide
• Two forms: amylose and amylopectin
• Most starch is 10-30% amylose and 70-90% amylopectin
• Branches in amylopectin every 12-30 residues
• Amylose has alpha(1→4) links, one reducing end
• The branches in amylopectin are α(1→6).
Amylose and Amylopectin
Amylose and amylopectin are two forms of starch. Amylopectin is
highly branched, with branches occurring every 12 to 30 residues.
Structure of Amylose
• Amylose is poorly soluble in water, but
forms micellar suspensions
• In these suspensions, amylose is helical
• Iodine fits into the helices to produce a
blue color
• Suspensions of amylose in water adopt a
helical conformation. Iodine (I2) can fit
into the hydrophobic middle of the
amylose helix to give a blue color that is
characteristic and diagnostic for starch.
Why Branching in Starch?
Consider the phosphorylase reaction
• Phosphorylase releases glucose-1-P products from the amylose
or amylopectin chains
• The more branches, the more sites for phosphorylase attack
• Branches in amylopectin provide a mechanism for quickly
releasing glucose units for energy metabolism
The Phosphorylase Reaction Releases
Glucose Units for Metabolic Energy
The starch phosphorylase reactions cleaves glucose residues from
amylose, producing α-D-glucose-1-phosphate, an energy source
for the organism.
Glycogen
The glucose storage device in animals
• Glycogen constitutes up to 10% of liver mass and 1-2% of
muscle mass
• Glycogen is stored energy for the organism
• Only difference from amylopectin: even more highly branched
• Alpha(1,6) branches every 8-12 residues
• Like amylopectin, glycogen gives a red-violet color with iodine
Dextrans
A small but significant difference from starch and glycogen
• If you change the main linkages between glucose from alpha(1,4) to
alpha(1,6), you get a new family of polysaccharides - dextrans
• Branches can be (1,2), (1,3), or (1,4)
• Dextrans formed by bacteria are components of dental plaque
• Dextrans in plaque presumably provide protection for oral bacteria
• Cross-linked dextrans are used as "Sephadex" gels in column
chromatography
• These gels, used to separate biomolecules on the basis of size, are
up to 98% water!
Structural Polysaccharides
• The composition of structural polysaccharides is similar to
storage polysaccharides
• But small structural differences greatly influence properties
• Starch and glycogen linkages consist primarily of α(1→4)
linkages.
• Cellulose consists of β(1→4) linkages
Structural Polysaccharides
• Cellulose is a structural polysaccharide, provides physical
structure and strength to plants
• It is the most abundant natural polymer in the world
• It is found in the cell walls of nearly all plants
• The wood and bark of trees are insoluble, highly organized
structures formed from cellulose and lignin
• Cotton is almost pure cellulose
• Cotton acetates, made from the action of acetic anhydride on
cellulose, are used in dresses, lingerie, and other clothing
The Structural Difference Between
Amylose and Cellulose
(a) Amylose prefers a helical conformation (due to its bent α(1→4)
linkages. (b) Cellulose, with β(1→4) linkages, can adopt a fully
extended conformation.
The Structure of Cellulose
The structure of
cellulose,
showing the
hydrogen bonds
(blue) between
the sheets,
which
strengthen the
structure.
Intrachain H-
bonds in red;
interchain H-
bonds in green.
Q&A
