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CARBOHYDRATES (Structures and Functions) ...

structure

Carbohydrates The numbering system


• Aldehyde or ketone derivatives of polyhydric (more than one - For an aldose the carbonyl carbon is always carbon #1.
OH group) alcohols or as compounds that yield this derivative on When the aldose is drawn in a Fischer projection you would
hydrolysis. continue to number the carbon as you go down the cahin
•Polyhydroxy aldehydes or ketones and their derivatives
...structure (nomenclature)
• Empirical Formula (CH2O)n
• (HCOH)n
*Note the structure of aldehyde and ketone.
n- correlates to the overall size of the monosaccharide
Aldo- or Keto- are used followed by the numerical prefixes
attached to an -ose
Biological Importance
Glucose- most important carbohydrate *with structure
-bulk of dietary carbohydrate absorbed in the *with structure
bloodstream
The Fischer projection
-can be source of all carbohydrates in the bidy
• An open chain form with the most highly oxidized oxygen at or
- major fuel of the tissues of mammals and a universal fuel
near the top
of the fetus
Note: with double bonds - highly reactive and unstable
Glycogen- for storage
*glucose structure
Ribose- in nucleic acids
The Haworth projection (cyclic structure)
Galactose- in milk, in certain complex lipids, and in combination
• due to the condensation of the carbonyl with a hydroxyl
with protein in glycoproteins and proteoglycans
carbon of pentoses and hexoses to form an internal hemiacetal
or hemiketal producing a cyclic structure
Diseases associated with CHO • the predominant form and is in equilibrium with the open-
1. DM chain (linear) form
2. Galactosemia
*with structure
3. glycogen storage diseases
*hemiacetal and hemiketal structure
4. lactose intolerance
The Boat and Chair conformation

Classification
Stereoisomerism of Monosaccharides
•Monosaccharides- cannot be hydrolyzed into simple CHO e.g.
Stereoisomers- are compounds in which the atoms are linked in
glucose, glycerose, erythrose
the same order but differe in their spatial arrangement
•Disaccharides- yields two molecules of disaccharides when
Enantiomers – compounds that are mirror images of each other.
hydrolyzed e.g. sucrose
*with table
•Oligosaccharides- yields two to ten monosaccharide units on
...stereoisomerism
hydrolysis e.g. maltotriose
•Polysaccharides- yields more than 10 monosaccharide units on
hydrolysis e.g. starch, dextrin Asymmetric carbon atom-carbon atom attached to four (4)
different atoms or groups
•Number of possible isomers of a compound= 2n
Monosaccharides (Basic Structure)
•where n- is the # of asymmetric carbon atoms
• The basic feature that makes an aldose different from a ketose
is the position of the carbonyl group of monosaccharide. An
aldose has a carbonyl group at carbon #1 (affording an Types of Isomerism

aldehyde) while a ketose has a carbonyl group at carbon #2 1. D and L

(affording a keone) •The designation of an isomer as the D form or its mirror image as

* with figure
the L form is determined by its spatial relationship to the parent the same number of carbon, hydrogen and oxygen molecules
compound of the carbohydrate family e.g. glucose and fructose

-the three (3) carbon sugar glycerose

•The orientation of the -H and the -OH groups around the Monosaccharide Derivatives
carbon atom adjacent to the terminal primary alcohol carbon •Glycosides
(e.g. C5 in glucose) determines whether the sugar belongs to the -are formed as a result of further condensation between the
D or L series. In the “D” sugars, the hydroxyl group on the hydroxyl group on the anomeric carbon of the sugar and the
asymmetric carbon furthest from the carbonyl group is the hydroxyl group of a second molecule to form an acetal
“right” in the fischer projection
e.g. glucosides, fructosides
*with table
*glycosidic bonds- stabilize the cyclic form
•The presence of asymmetric carbon atoms confers optical
If the second molecule is a sugar, the glycoside is a
activity on the compound
disaccharide; if it is a disaccharide, the glycoside is a
Dextrorotatory-rotates the beam of polarized light to the right (+)
trisacharide and so on.
Levorotatory-rotates the beam of polarized light to the left
*..glycosides structure
Racemic - equal amounts of D and L isomers present
The glycosidic bond can be with nonsugar alcohols such as
2. Pyranose and Furanose Ring Structure
methyl alcohol to give a-Methyl glucoside.
Formation of 5-membered (pyranose) and 6-membered
*with structure
(furanose) ring structures due to the reaction between an
aldehyde of a ketone group and an alcohol to form a
hemiacetal or a hemiketal. •N-Glycosylamines (N-Glycosides)

*pyran and furan ring structures -formed from the reaction of aldoses and ketoses with amines in
an appropriate solvent
3. Alpha and Beta Isomers
Isomeric forms monosaccharides that differ from each other only -also called N-glycosides

in the configuration about the carbonyl carbon; that carbonyl importance: in the nucleotides and nucleic acid ring nitrogen
carbon is called the anomeric carbon. atoms of purine or pyrimidine bases which form N-glycosylamine
So, from a fischer projection of monosaccharide, we can draw linkage with carbon atom 1 of D-ribose or 2-deoxy-D-ribose
two possible cyclic forms (Haworth), the alpha and the beta

*with structure
•Sugar alcohols
* Note: directed downward - alpha
-formed by the reduction of the carbonyl group of
directed upward- beta
monosaccharides by H2 gas in the presence of metal catalysts
or by sodium amalgam in water.
Cyclic monosaccharide structures and anomeric forms examples: D-glucitol from glucose

•Cyclic forms possess anomeric carbons D-mannitol from D-mannose


•For D-sugars, alpha has OH down, beta up
importance:
•For L-sugars, the reverse is true
glycerol- an important component of some lipids
4. Epimers
inositol- found in the lipid phosphotidyl inositol and in phytin,
Isomers differing as a result of variations in the configuration of
which is abundant in the extracellular supporting material in
the -OH and –H on carbon atoms 2, 3 and 4 of glucose
higher plant tissues
Two sugars differing only in the configuration around one specific
*with table
carbon atom are calles epimers of each other
•Sugar acids
* Epimerization of Glucose(drawing)
Aldonic acids- formed by the oxidation of the aldehydic carbon
*Galactose is the epimer of glucose in the 4th carbon
atom by weak oxidizing agents, or by specific enzymes to form
mannose is the epimer of glucose in the 2nd carbon
the corresponding carboxylic acids
5. Aldose-KetoseIsomerism
•Presence of a potential ketose or aldose group in a sugar with
ex. -D-gluconic acid from glucose, which in phosphorylated form amylases on starch
is an important intermediate in carbohydrate metabolism -contains two D-glucose residues; both glucose molecules are in
the pyranose form, and the configuration at the anomeric
Aldaric acid- formed by the oxidation of both the aldehydic
carbon atom in glycosidic linkage is alpha
carbon and the carbon atom bearing the primary hydroxyl
*maltose structure
group to a carboxyl group by the action of a stronger oxidizing
agent, e.g. nitric acid -the first glucose cannot undergo oxidation, but the second can,
since the second residue has a free anomeric carbon atom
Ex. D-glucaric acid from D-glucose
capable of existing in alpha or beta form---thus is called the
Uronic acid- formed by the oxidation of the carbon atom
reducing end
bearing the primary hyrdroxyl group to a carboxyl group
-glycosidic linkage is 1 ->4
ex. -D-glucuronic acid, D-galacturonic acid, D-mannuronic acid
*wit structure
Importance: components of many polysaccharides
O-glycosidic bond
*with structure
2. Lactose (galactose and glucose) wala napicturan, sorry. Si
•Sugar phosphates
doc b kadasig. ^__^”
-phosphate derivatives of monosaccharides
*structure
-serve as an important intermediates in carbohydrate
3. Sucrose (glucose and fructose)
metabolism
-cane sugar, table sugar
*with structure
-extremely abundant in the plant world
•Deoxysugars
-contains no anomeric carbon; the anomeric carbon atom of
-are those in which the hydroxyl group attached to the ring
the two hexoses are linked to each other
structure has been replaced by a hydrogen atom
-more readily hydrolyzed than the other disaccharides
Ex. -2-deoxyribose – the sugar component of DNA -hydrolysis yields a crude mixture called “invert sugar”

L-fucose (6-deoxy-L-galactose)- important component of some *with structure

bacterial cell wall 4. Cellobiose -repeating disaccharide units of cellulose

..deoxysugars structure -contains two D-glucose units


-has a B-(1->4) glycosidic linkage
-O-B-D-Glucopyranosyl-(1->)-B-D-glucopyranoside
•Amino sugars
*with structure
The hydroxyl group at carbon 2 is replaced by an amino group
*ang B is beta sign na sia tni,di ko mkita ang symbol
Ex. -D-glucosamine -occurs in many polysaccharides
of vertebrate tissue and is a major component of chitin
5. Trehalose – contains two D-glucose residues
-D-galavtosamine – component of glycolipids and of the major -another example of a non-reducing disaccharide in which the
polysacchsaride of cartilage, chondroitin sulfate anomeric carbon atoms are joined
*...amino sugars structure -major sugar found in the hemolynph of many insects

•Muramic and Neuraminic acid -O-a-D-glucopyranosyl- (1->1)-a-D-glucopyranoside

-A six carbon sugar linked to a three-carbon sugar sugar acid-


are important building blocs of the polysaccharides found in cell OLIGOSACCHARIDES

walls of the bacteria and the cell coats of other animal cells • composed of two to ten monosaccharide units

Ex. –N-acetylmuramic acid and N-acetylneuraminic acid


POLYSACCHARIDES
• are polymers of simple sugars
DISACCHARIDES
• form in which most of the carbohydrates are found in nature
• are sugars composed of two monosaccharide residues united
• on complete hydrolysis with specific acid or specific enzymes,
by a glycosidic linkage
yield monosaccharides and/or monosaccharide derivatives
• their chemical name reflects their component • monosaccharide derivatives commonly found as structural
monosaccharides units of natural polysaccharides
1. Maltose -formed as an intermediate product of the action of
-D-glucosamine, D-galactosamine, N-acetylmuramic acid •Branches provide a mechanism for quickly releasing (or storing)
and N-acetylneuraminic acid glucose units for (or from) metabolism
• Glycans- differ in length of chain and in the degree of *with structure
branching
Enzymes (for hydrolysis of glucose)
Homopolysaccharide-contain only one type of monomeric unit •a-amylase – [a (1->4)-glucan 4-glucanohydrolase]
e.g. Starch, glycogen, cellulose -present in saliva and pancreatic juice
Heteropolysaccharide- contain 2 or more monomeric units -participates in the digestion of starch in the gut
e.g. hyaluronic acid (contain alternating residues of D-glucorinic -hydrolyzes a-(1-4) linkages at random to yield glucose and free
acid and N-acetyl-D-glucosamine) maltose
Functions: storage, structure, recognition
Starch and glycogen are storage molecules • B-amylase – [a(1->4)-glucan 6-glucanohydrolase]
Chitin and cellulose are structural molecules -enzyme found in malt
Cell surface polysaccharides are recognition molecules -cleaves away successive maltose units beginning from the
nonreducing end to yield maltose quantitatively
Storage Polysaccharides
1. Starch -Both a- and B-amylases can also attack amylopectin
-a plant storage polysaccharide Dextrin- polysaccharide of intermediate chain length that are
-formed of an a-glucosidic chain formed from starch components by the action of the amylases
-yields only glucose on hydrolysis, thus called a glucosan or
glucan Limit dextrin-represents the limit of the attack of amylases,
-2 forms:amylase and amylopectin because the a- and B- amylases cannot hydrolyze the a(1->6)
Amylose linkages at the branch points of amylopectin
• 15-20%
•consists of long unbranched chain in which all the D-glucose Debranching enzyme – [a(1->6)glucan 6-glucanohydrolase, also
residues are bound in a(1->4) linkages called a(1->6)-glucosidase
•has one reducing end • can hydrolyze the a(1->6) linkakpges at the branch points
•consists typically of 200 a 20,000 units which form a helix as a
result of the bond angles between the glucose units 2. Glycogen
•poorly soluble in water, but forms micellar suspensions • main storage polysaccharide of animal cells
•In these suspensions, amylose is helical • often called animal starch
-iodine fits into the helices to produce a blue color • constitues up to 10% of liver mass and 1-2% of muscle mass
• glycogen is stored energy for the organism
Amylopectin • only difference from stach: number of branches
•80-85% • Alpha (1->6) branches every 8-12 residues
•highly branched •Like amylopectin, glycogen gives a red-violet color with iodine
•branches in every 24 -30 glucose residues
•a(1->4) linkages in the chains and a(1->6) linkages at the The glucose chains are organized globularly like branches of a
branch points tree originating from a pair of molecules of glycogenin, a protein
•may contain up to 2 million glucose units with a molecular weight of 38,000 that acts as a primer at the
With structure core of the structure. Glycogen is easily converted back to
glucose to provide energy
Why branching in starch? *with structure
Consider the phosphorylase reaction..
•Phosphorylase releases glucose 1-P products from the amylose 3. Dextrans
or amylopectin chains A small but significant difference from starch and glycogen
•The more branches, the more sites for phosphorylase attacks -if you change the main linkages between glucose from alpha
(1,4) to alpha (1,6) you get a new family of polysaccharides-
dextrans •HETEROPOLYMERS
-branches can be (1,2) , (1,3), (1,4) Glycosaminoglycans
-dextrans are formed by bacteria are components of dental -are negatively charged, highly viscous molecules sometimes
plaque called mucopolysaccharides
-cross-linked -the physiologically most important glycosaminoglycans are:
*used in chromatography *Hyaluronic acid *Dermatan sulfate
*Chondroitin sulfate *Heparin
STRUCTURAL POLYSACCHARIDES *Heparin sulfate *Keratan sulfate
Polymeric carbohydrates are major structural components in
a. Plant and bacterial cell walls -are long unbranched polysaccharides composed of repeating
b. extracellular matrix of vertebrates disaccharide units in which one of the two sigars is either N-
acetylglucosamine or n-galactosamine
-are highly negatively charged due to the presence of carboxyl
STRUCTURAL POLYSACCHARIDES INCLUDES or sulfate groups on many of the sugar residues
a. homopolymers -are usually found in extracellular space in multicellular
b. heteropolymers organisms, where they produce a viscous matrix that resists
compression
•Monosaccharides that are used to build other polysaccharides
D-mannose Benefits
D- and L- galactose a. can provide passageway for cell migration
D-xylose b. lubrication between joints
L-arabinose c. rigidity to structures such as cartilage or ball of the eye
D-glucurinic acid
L-iduronic acid Chondroitin Sulfate
N-acetyl-D-glucosamine -is composed of B-D-glucoronated linked to the third carbon of
N-acetyl-D-galactosamine N-acetylgalactosamine-4 sulfate
N-acetylneuraminic acid
Heparin
• HOMOPOLYMERS -a complex mixture of linear polysaccharides
1. Cellulose -have anticoagulant properties
-most abundant natural polymer on earth Other Structural Polysaccharides
-is the principal strength and support of trees and plants Alginates- Ca-binding polymers in algae
-it can also be soft and fuzzy just like a cotton Agarose and agaropectin- galactose polymers
-is a polymer of B-D-Glucose Glycosaminoglycan – repeating disaccharides with amino
-in contrast to starch, is oriented with CH2OH groups alternating sugars and negative charges
above and below the plane of the cellulose molecule thus
producing long, unbranched chains Agar and Carrageenan
-the absence of side chains allow cellulose molecules to lie • Agar is extracted from seaweed and is used in many foods as
close together and form rigid structures gelling agent, agar is a polymer of agarobiose, a disaccharide
*with structure composed of D-galactose and 3,6-anhydro-L-galactose. Highly
refined agar is used as a medium for culturing bacteria, cellular
2. Chitin tissues, and for DNA fingerprinting.
-exoskeletons of crustaceans, insects and spiders, and cell walks
of fungi • Carrageenan is a generic term for several polysaccharides also
-similar to cellulose, but C-2s are N-Acetyl extracted from seaweed. Carrageenan compounds differ from
-cellulose strands are parallel, chitins can be parallel or agar in that they have sulfate groups (-OSO3) in place of some
antiparallel hydroxyl groups. Carrageenan is also used for thickening,
suspending and gelling food products.