CN 112 – BIOCHEMISTRY 1ST EXAM REVIEWER o contain a single polyhydroxy aldehyde or polyhydroxy ketone

unit
 Carbohydrates
o cannot be degraded into simpler products by hydrolysis
 the most abundant class of bioorganic molecules on earth
reactions
 produced by the photosynthetic activity of the green plants
o pure monosaccharides are water-soluble, white, crystalline
 also referred to as saccharides because of the sweet taste of many
solids
carbohydrates
- Disaccharides
 (Latin, saccharum, meaning sugar)
o contains 2 monosaccharide units covalently bonded to each
 storehouse of chemical energy (glucose, starch, glycogen)
other
- a gram of digested carbohydrate gives about 4 kcal of energy
o crystalline and water soluble substances
- complex carbohydrates are best for diet
o upon hydrolysis they produce monosaccharides
 supportive structural components in plants and some animals (cellulose,
chitin) - Oligosaccharides
 form part of the structural framework of DNA & RNA o contains 2-10 monosaccharide units – covalently bonded
 carbohydrate “markers” on cell surfaces play key roles in cell-cell o disaccharides are the most common type
recognition processes. o trisaccharides (raffinose)
 Classification of Carbohydrates o tetrasaccharides (stachyose)
 Simpler Formula: – o free oligosaccharides, other than disaccharides, are less
- CnH2nOn or Cn (H2O)n (hydrates of C) common in nature
- n= number of atoms o usually found associated with proteins and lipids in complex
 polyhydroxy aldehydes or polyhydroxy ketones or compounds that molecules that serve structural and regulatory functions
produce such substances upon hydrolysis. - Polysaccharides
o consist of tens of thousands of monosaccharide units
covalently bonded
o homopolysacchrides – polymers of a single monosaccharide
(glycogen, cellulose, starch)
o heteropolysaccharides – contain more than one kind of
monosaccharide (hyaluronic acid, heparin, chondroitin
sulfate)
- Derived carbohydrates
o those where carbohydrate moieties have undergone some
reactions converting them into other products
o sugar acids, sugar alcohols, deoxysugars, and sugar amines
 Classification based on products of acid hydrolysis:
 Classification of Monosaccharides
- Monosaccharides
 carbohydrates that have the general formula CnH2nOn
o the simple sugars
- n varies from 3 – 8.
 grouped together according to the number of carbons they contain: o the parent member of the family of monosaccharides
- C3H6O3 – triose o from them emanates the other members of the monosaccharide
- C4H8O4 – tetrose family.
- C5H10O5 – pentose o the final form of carbohydrate into which all carbohydrates,
- C6H12O6 – hexose regardless of their complexity, are degraded in the body during
- C7H14O7 – heptose carbohydrate metabolism.
- C8H16O8 – octose o D(+)- glyceraldehyde – an aldotriose
 may either be: o Dihydroxyacetone – a ketotriose
o an aldose – contains aldehyde group  Pentoses
o a ketose – contains ketone group o Aldopentoses
 D-(-)-lyxose - a constituent of the heart muscle
 D-(-)-ribose - ribose and 2-deoxyribose–present as
intermediates in metabolic pathways and are important
building blocks of RNA and DNA.
o Ketopentoses
 D-ribulose
 D-xylulose
 Hexoses
 presence of a ketone group is usually indicated by using the ending o the most common of all the monosaccharides.
“___ulose” in naming the sugar o Aldohexoses
o e.g., levulose  D-(+)-mannose
 D-(+)-glucose - A 5% (m/v) glucose solution is often used
in hospitals as an intravenous source of nourishment for
patients who cannot take food by mouth.
 D-(+)-galactose
o Ketohexose
 D-(-)-fructose
o D-mannose
 found in certain bacteria, fungi, and plants
 converted to usable glucose in the body, but has no real
physiological significance
 Monosaccharides can be classified based on their spatial orientation
(stereochemistry).

 Trioses
  A monosaccharide can be classified as a D or L isomer, depending on the
spatial orientation of the –H and –OH groups attached to the carbon atom
adjacent to the terminal primary alcohol group.
 The D isomer is represented when the –OH is written to the right of this
carbon in the Fischer projection formula. The L isomer is represented
when this –OH is written to the left.
 Biochemically Important Monosaccharides:
 Glucose and Fructose
o Most abundant in nature
o Nutritionally most important
o Grape fruit good source of glucose (20 - 30% by mass) -- also
named grape sugar, dextrose and blood sugar (70 - 100 mg/100
mL of blood)
o Six membered cyclic form:
1. Ketohexose
2. Sweetest of all sugars; the fruit sugar
3. Found in many fruits and in honey
4. Good dietary sugar-- due to higher sweetness
5. Five membered cyclic form
 Galactose
o A component of milk sugar
o Synthesized in human
o Also called brain sugar-- part of brain and nerve tissue
o Used to differentiate between blood types
o Six membered cyclic form
o Galactosemia - a result of genetic deficiency in the infant – the
gene responsible for the enzyme that converts D-galactose to D-
glucose. Such infants cannot metabolize galactose and it builds up
in the blood and tissue.
 Ribose
o Part of RNA
o Part of ATP
o Part of DNA
o Five membered cyclic form
 Cyclic Forms of Monosaccharides:
 Hemiacetals and Hemiketals
o The dominant form of monosaccharides with 5 or
more C atoms is cyclic
o Hemiacetals and hemiketals are formed from the
reaction between two functional groups:
aldehyde or ketone and alcohol
 may take place either intermolecularly or
intramolecularly as in the case of sugars,
provided there are sufficient number of
carbons between the aldehyde or ketone
and the alcohol group to permit a stable
ring formation
 five- or six-membered hemiacetal rings are stable
o Two types of ring structures are possible:
 five-membered ring, or furanose ring, derived from
parent compound furan
 six-membered ring, or pyranose ring, derived from parent
compound pyran
 o All aldoses with five or more carbon atoms establish similar
equilibria, but with different percentages of the alpha, beta, and
 Cyclic Hemiacetal Forms of D-Glucose
open-chain forms.
o In the cyclic hemiacetals of glucose, C1 * , is now a chiral center
o Fructose and other ketoses with a sufficient number of carbon
(an anomeric carbon)
atoms also cyclize.
 two anomers of D-glucose: -D-glucose & -D-glucose
 Reactions of Monosaccharides:
o The cyclic hemiacetals are readily interconvertible in aqueous
 Five important reactions of monosaccharides:
solution o Oxidation to acidic sugars
 this intercoversion of - and - anomers in solution is
o Reduction to sugar alcohols
accompanied by a change in specific rotation called
o Phosphate ester formation
MUTAROTATION.
o Amino sugar formation
 only sugars that form hemiacetal or hemiketal structure
o Glycoside formation
mutarotate.
o 2 anomeric forms of D-glucose:
 Alpha-form: -OH of C1 and CH2OH of C5 are on opposite
sides
 Beta-form: -OH of C1 and CH2OH of C5 are on same sides
 These reactions will be considered with respect to glucose; other aldoses,
o Anomers: Cyclic monosaccharides that differ only in the position
as well as ketoses, undergo similar reactions.
of the substituents on the anomeric carbon atom  Oxidation
o Any —OH group at a chiral center that is to the right in a Fischer o Gives three different types of acidic sugars depending on the type
projection formula points down in the Haworth projection of oxidizing agent used:
formula and any —OH group to the left in a Fischer projection  Weak oxidizing agents like Tollens and Benedict ’s
formula points up in the Haworth projection formula. solutions oxidize the aldehyde end to give an aldonic acid.
 Strong oxidizing agents can oxidize both ends of a
monosaccharide at the same time to produce aldaric acid.
 In biochemical systems enzymes can oxidize the primary
alcohol end of an aldose such as glucose, without
 oxidation of the aldehyde group, to produce an alduronic
acid.

 Reduction  Redox Reactions of Monosaccharides:

o The carbonyl group in a monosaccharide (either an aldose or a
ketose) is reduced to a hydroxyl group using hydrogen as the
reducing agent.
 product is the corresponding polyhydroxy alcohol, sugar
alcohol
 e.g., Sorbitol (glucitol) - used as moisturizing agents in
foods and cosmetics and as a sweetening agent in
chewing gum
o Under prescribed conditions, some sugars reduce silver ions to free silver
and copper(II) ions to copper(I) ions. Such sugars are called reducing
sugars.
o A reducing sugar will have one of the following groups:
 an aldehyde group (as in glyceraldehyde)
 a hydroxyketone (as in fructose)
 a cyclic hemiacetal group (as in glucose and maltose)
o The Benedict, Barfoed, and Fehling tests are based on the formation of a
brick red copper(I) oxide precipitate as a positive result while the Tollens
test is based on the formation of a silver mirror.
o The Barfoed test is more sensitive in that it can distinguish a reducing
monosaccharide from a reducing disaccharide.
o The sugars are oxidized to carboxylic acids and the metal ions are reduced