BIOCHEMISTRY

CARBOHYDRATE CHEMISTRY LE2

DIGESTION, ABSORPTION & TRANSPORT
Dr. Catherine C. Donato || 10/05/2017

OUTLINE  They are structural components of many organisms like:

I. CHO Chemistry V. Polysaccharides  Fiber of plants (cellulose)
A. Definition VI. Test for Sugars  Exoskeleton of some insects and crustaceans (chitin)
B. Functions VII. CHO Digestion  Cell wall of microorganisms
C. Structure A. Salivary and Pancreatic  Cell membrane: glycoproteins and antigens
D. Cyclization of Sugars Amylase  Carbohydrates also serve as the storage form of energy
E. Classifications B. Disaccharidases (glycogen) to meet the immediate energy demands of the body
II. Definition of terms C. Absorption of Sugars
A. Stereoisomers D. Dietary Fiber C. STRUCTURE
B. Epimers VIII. Glucose Transport Proteins
C. D- and L- Sugars A. Na-Dependent
D. Aldose and Ketose Transporters
E. CHO Derivatives B. Facilitative Glucose
F. Reducing Sugars Transporters
G.Glycoside IX. Glucose Transport
H. Isomerism Through the Blood-Brain
III. Monosaccharides Barrier
A. Classification X. Clinical Correlations
B. Biologically Important
Examples
IV. Disaccharides
A. Disaccharide Formation Figure 1. Fischer Projection (right) vs. Haworth Projection (left)
B. Biological Important
Examples  Composed of carbon, hydrogen and oxygen atoms
 Can be drawn in:
 Fischer projections - show sugars in the open chain form.
OBJECTIVES The carbon atoms of a sugar molecule are connected
 Discuss CHO breakdown from dietary sources vertically by solid lines while C-O and C-H are connected
 Recognize features of carbohydrates horizontally
 Illustrate the structure of glucose and other biologically important  Haworth projection - shows the cyclic structure of sugars
sugars with a simple three-dimensional perspective
 Describe the main stages of digestion  Chair conformation - the most stable conformation because
 Discuss mechanisms involved in the absorption of nutrients from the it minimizes steric hindrance and torsional strain
digestive tract
 Discuss the role of the digestive enzymes

I. CARBOHYDRATE CHEMISTRY

A. DEFINITION

 Carbohydrates are the most important source of energy for the

body
 Often converted to common molecule: glucose, which
functions as an energy source
 most abundant organic molecules in nature
 polyhydroxy aldehydes or ketones Figure 2 Conversion of Haworth projection to Chair conformation.
 Contain three elements - C, H, O, many according to the
formula (CH2O)n; where n ≥ 3  Most sugars in the solution are in the ring configuration or chair
 Three major classes: conformation structure
 Monosaccharides  From the linear or open structure, it will be transformed into a
 Disaccharides ring structure
 Polysaccharides  Carbonyl carbon in the open chain form (Fischer Projection)
becomes an anomeric carbon when it is cyclized (Haworth
B. FUNCTIONS Projection or Chair Conformation)
 Only Sugars with ≥ 5 C mostly exist in their cyclized form
 Carbohydrates are the most abundant dietary source of (intramolecular hemiacetal formation):
energy (4cal/g) for all organisms.  Anomers: Isomeric forms that differ only in their
 Carbohydrates are precursors for many organic compounds configuration about the hemiacetal or hemiketal carbon atom.
such as fats and amino acids (DNA). ⇒α and β anomers
 Carbohydrates (as glycoproteins and glycolipids) participate in  Two “chair” conformations (conformers).
the structure of cell membrane and cellular functions such  Conformers with bulky groups in equatorial postions are
as cell growth adhesion and fertilization. favored (Less steric hindrance; fewest repulsive interactions)
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 II. DEFINITION OF TERMS

A. STEREOISOMERS

 Compounds with the same molecular formula and attachments

but have different orientations in space.

B. EPIMERS

 Compounds with more than one chiral center but differ from
each other in the absolute configuration at only one chiral
Figure 3 Two possible chair conformations (note: axial and equatorial
placements of funcitonal groups).
center.
 A sub-group of stereoisomers
D. CYCLIZATION OF SUGARS
 Monosaccharides with five or six carbons are predominantly
found in a ring (cyclic) form
 Cyclic sugars are formed when an aldehyde (or ketone)
group has reacted with an alcohol group on the same sugar,
making the carbonyl carbon (C1 for aldose, C2 for ketose)
asymmetric
 reaction forms hemiacetals (aldoses) and hemiketals
(ketoses).
 Cyclic sugars that contain a five membered ring are called
furanoses
 Cyclic sugars that contain a six membered ring are called
pyranoses
 Cyclization creates an anomeric carbon (the new chiral C)
 The anomeric carbon is C1 in pyranose, and C2 in furanose.
 Cyclic sugars can be classified as α or β depending on the location
of the OH group attached to the anomeric carbon Figure 5. Structures of D-mannose, D-glucose and D-galactose
 If the hydroxyl group of the anomeric carbon, C1 in aldolases
and C2 in ketoses, is drawn downwards, then it is in the α  D-mannose and D-glucose are C2 epimers. They have
position. If it is drawn upwards, then it is in the β position exactly the same structure except at the second carbon where
–OH group is located on the left in D-mannose and –OH group
is located on the right in D-glucose.
 D-glucose and D-galactose are C4 epimers. They have
exactly the same structure except at the fourth carbon where –
OH is located on the right in D-glucose and –OH group is
located on the left in D-galactose.
 Importance of epimers is seen in specialized medications
 In pharmaceuticals where they modify the medications so
that it is specified for a specific symptom and the adverse
effects are lower.

C. D- and L-Sugars (Enantiomers)

 Sugars may be in D or L configuration

 It is determined by the position of the hydroxyl group on C5 or
Figure 4. Cyclization of Glucose the penultimate carbon.
 D-configuration: -OH is on the right
Note:  L-configuration: -OH is on the left
In converting the CHO from Fischer Projection to Haworth Projection,  D- and L- sugars are mirror images of each other but not
the OH of C5 is attached to C1 superimposable – they are enantiomers
 Most sugars in humans are in D-series

E. CLASSIFICATION

 Carbohydrates can be classified by the number of

monosaccharides (such as glucose) joined through glycosidic
bonds
 Monosaccharides - single sugar that contain at least 3
carbon atoms and one of which is a carbonyl carbon
 Disaccharides - formed when 2 monosaccharides are linked
together
 Oligosaccharides - formed when 3 to 12 monosaccharides
are linked together
 Polysaccharides - formed when many oligosaccharides are
linked together Figure 6. Structures of D-glucose and L-glucose

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 D. ALDOSE AND KETOSE (Functional isomers) G. REDUCING SUGARS

 Aldose – if the carbonyl carbon (C=O) is located in carbon 1  Have free anomeric carbon; capable of transferring hydrogen
 Aldose contains an aldehyde group ions to other compounds
 Ketose – if the carbonyl carbon (C=O) is located in carbon 2  All monosaccharides are reducing sugars - the anomeric carbon
 Ketose contains a ketone group has an ─OH group and therefore can act as a reducing agent
and can donate electrons to another molecule
 Some disaccharides and polysaccharides are reducible - when
the oxygen on the anomeric carbon of a sugar is NOT attached
to any other structure.

Figure 7. Structures of Aldose and Ketose

 3 carbon in an aldose is called aldotriose; 3 carbon in ketose is

called ketotriose

COMPLETE NAMING OF SUGARS:

Anomer (α/β) + enantiomer (L/D) + prefix of sugar (gluco/fructo/etc)
+ type of ring structure (furan/pyran) + suffix (-ose)
Example: B-D-Glucopyranose. α-L-Fructofuranose

F. CARBOHYDRATE DERIVATIVES/SUGAR SUBSTITUTES

Figure 9. Sucrose, Lactose and Maltose structures
 Amino sugars (important in glycoprotein hormones) and
phosphate sugars are carbohydrate derivatives. They are
the products if you replaced the hydroxyl groups with amino H. GLYCOSIDE
group or phosphate group.
 Sugar derivatives, like Splenda, have the same structure with  A sugar is bound to another functional group via glycosidic
sucrose but three of the hydroxyl groups are substituted with bond
chloride making it much sweeter compared to the regular  Linkage or a covalent bond that joins a sugar molecule to
sucrose (600 times sweeter) another group
 Sugar phosphates are important in the transfer and storage of
energy
 For instance, after glucose is transported into cells, it is
phosphorylated by a hexokinase to form glucose 6-
phosphate. Glucose-6-phosphate can then enter a
number of metabolic pathways. The three that are
common to all cell types are glycolysis, the pentose
phosphate pathway, and glycogen synthesis. Figure 10. Lactose

 Lactose (formed by galactose – glucose)

 β-1,4 glycosidic bond between –OH group C1 of galactose in
β position (drawn upward) and C4 of glucose

I. ISOMERISM

Chirality
 Non-superimposability of molecules; also called handedness
(left and right hands are non-superimposable)
 Chiral Center – a carbon with 4 non-identical substituents
attached to it; all bonds to carbon must be in single bond only
 Predicts the number of stereoisomers ( n= number of C
Figure 8. Major Pathways of Glucose Metabolism  Aldoses have , ketoses
have where n is the
 Other derivatives: number of Carbon atoms. (half
 Sugar acids (oxidation of aldehyde and alcohol groups) will be L- and half will be D-).
 Aldonic, alduronic and aldaric acids  Aldohexose has two achiral
 Sugar alcohols or glycitols (reduction of aldehyde and carbons (C1 and
ketone group) C6).Ketohexose has three
 Deoxyribose: OH in C2 is replaced by H (in DNA) achiral carbons (C1, C2, and
C6)
 N-acetylated sugars: important in RBC membrane Figure 11. Chiral Carbon

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Isomers ANOMERS
 Two molecules with the same formula but with different  Similar to epimers, but differ on the anomeric carbon
chemical structures  Alpha: -OH group in anomeric carbon is down
 Beta: -OH group in anomeric carbon is up

Figure 12. Isomers

Figure 16. Anomers
Functional Isomers
 Constitutional Isomers that have the same chemical formula
but differs in functional groups OPTICAL ACTIVITY

 Ability of a chiral molecule to rotate plane-polarized light

 Chiral molecules rotate plane-polarized light
 Achiral molecules do not rotate plane-polarized light
 Dextrotatory (D) – clockwise rotation (+)
 Levorotatory (L) – counter clockwise rotation (-)
 It cannot be determined based on the structure alone. It is
determined through experimental procedures.
Figure 13. Smallest monosaccrides (C=3)
III. MONOSACCHARIDES
DIASTEREOMERS
 Non-superimposable, non-mirror image stereoisomer  All monosaccharides are reducing sugars
 Diastereomers of D-glucose – all aldohexoses except D-  Simplest form of carbohydrate
glucose; diastereomers of L-glucose – all aldohexoses  Cannot be broken down by hydrolysis
except L-glucose  Physical properties: Low molecular weight, soluble in water,
sweet to taste
 General Formula: CnHnOn
REDUCING SUGARS
• Can reduce oxidizing agents like Benedict’s, Barfoed’s, Tollens
reagent, Fehling’s reagent.
• Structurally contains a free -OH on the anomeric carbon

Figure 14. Diastereomers

A. CLASSIFICATION
ENANTIOMERS
 Chiral molecule Position of the Carbonyl Carbon
 Non-superimposable mirror image  Aldose = carbonyl carbon is C1 (Aldehyde)
 It occurs in D- or L- configurations  Ketose = carbonyl carbon is C2 (Ketone)
 L-glucose is an enantiomer of D-glucose
Aldose Ketose

D-Glucose L- Fructose
Figure 17. Fischer Projection
Figure 15. D-glucose and L-glucose are enantiomers

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 Number of Carbon Atoms
Table 1. Classification of Monosaccharides
# of
Term Aldehyde Ketones
Carbons
3 Trioses Aldotriose Ketotriose
4 Tetroses Aldotetrose Ketotetrose
5 Pentoses Aldopentose Ketopentose
6 Hexoses Aldohexose Ketohexose
7 Heptose Aldoheptose Ketoheptose

Figure 19. Cyclic Monosaccharides

B.BIOLOGICALLY IMPORTANT MONOSACCHARIDES

Erythrose
 Natural isomer: D-erythrose
 A tetrose saccharide
 Phosphorylated: Erythose-4-phosphate
 An intermediate in HMP shunt

Ribose
 Pentose monosaccharide
 β-D-ribofuranose forms part of the backbone of RNA
 It is related to deoxyribose, which is found in DNA.
Phosphorylated derivatives of ribose such as ATP and
NADH play central roles in metabolism.
Figure 18. Common examples of monosaccharides  cAMP and cGMP, formed from ATP and GTP, serve as
Other examples: Lyxose (aldopentose), Erythulose secondary messengers in some signalling pathways.
(ketotetrose). Xylulose (ketopentose
Glucose
Chiral Handedness ( D- / L-)
 Most stable: D-glucose
 In fischer projection, the –OH group at C5 or penultimate
 Also known as blood sugar (dextrose)
carbon (both aldoses and trioses) determines the configuration.
 Most common energy source
 Handedness of monosaccharides depend on chiral center
farthest from the carbonyl carbon (last chiral center)
Galactose
 Most sugars in human are in D configuration
 C4 epimer of D-glucose
 ─OH points to RIGHT = sugar is D
 Synthesized from glucose in mammary glands for use in
 ─OH points to the LEFT = sugar is L
lactose
 D-galactose is sometimes called brain sugar - it is a
component of glycoprotein found in brain and nervous tissue

Figure 18. Glucose Stereoisomers

Cyclic Forms Figure 20. Structure of Galactose

 Ring formation occurs because aldehydes and ketone groups Mannose
react reversibly with hydroxyl groups in an aqueous solution;  C2 epimer of glucose
occurs spontaneously  Constituent of many glycoproteins
 5-membered ring = furanose  Seldom encountered as free monosaccharide
 6-membered ring = pyranose  Also known as the bitter sugar

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 III. Amino Sugars
 contain an NH2 group in place of an ─OH group
 Galactosamine is a glycoprotein hormone, examples are
follicle-stimulating hormone (FSH) and luteinizing hormone
(LH).
 An example of glucosamine is chitin which is a component of
the exoskeleton of invertebrates.

Figure 21. Structure of Mannose

Fructose
 Different from glucose in C1 and C2
 A furanose
 Isomer of glucose, galactose, and mannose
 Also known as fruit sugar
 Can be easily phosphorylated at C1 or C6 (Fructose-1,6- Figure 24. Structure of Amino Sugars
bisphosphate)
 Can be converted into glucose in the liver for metabolic IV. DISSACHARIDES
purposes  Composed of two monosaccharides connected by a glycosidic
 C2 is the reducing end (most oxidized carbon) linkage
 General formula: CnH2(n-1)On-1
 Usually formed by Hexoses ( C12H22O11)
 Formed by condensation reaction (dehydration)
 Breaking apart a double sugar into its two simple sugars is
accomplished by hydrolysis with the help of a type
of enzyme called a disaccharidase.
 It down consumes a water molecule. These reactions are vital
in metabolism.
 Each disaccharide is broken down with the help of a
corresponding disaccharidase (sucrase, lactase, and maltase).
Figure 22. Structure of Fructose
A. DISSACHARIDE FORMATION
Sugar Substitutes
I. Glucose-6-Phosphate
Reducing Sugars
 When the oxygen on the anomeric carbon of a sugar is NOT
 Important in the storage of sugar
attached to any other structure
 Four fates of G6P:
 Only the state of the oxygen on the anomeric carbon determines
 converted to glucose (gluconeogenesis)
if the sugar is reducing or non reducing - the other hydroxyl
 converted to glycogen (glycogenesis)
groups on the molecule are not involved
 converted to pentose phosphates
 All 1,1 glycosidic bonds are non-reducing sugars (if both aldose)
 hydrolyzed to pyruvate (glycolysis)
 Sucrose: Non-reducing (1,2) because C2 is anomeric in ketoses

Figure 23. Structure of G6P

II. N-acetylneuraminic acid (NANA)

 the predominant sialic acid found in mammalian cells
Figure 25. Reducing Sugars
 This negatively charged residue is found in glycoproteins
found at the cell membrane.
 Prevents clumping of RBCs
Glycosidic Bond
 Glycosides are formed by condensation between the hydroxyl
group of the anomeric carbon of a monosaccharide and a
second compound, which may or may not be a
monosaccharide.
 Covalent bond formed between monomeric sugars in a
carbohydrate chain.
 Two types of glycosidic bonds:
 O-glycosidic bond: bonded to O
Figure 23. Structure of NANA  N-glycosidic bond: bonded to N

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 Figure 27. Structure of Lactose

Maltose
 Glucose + Glucose
 Bond: a-1,4 linkage between C1 of a-D-glucopyranose and
C4 of a-D-glucopyranose
 Broken down by: Maltase
 Also known as malt sugar
 Is a reducing sugar
Figure 26.A. Example of O-Glycosidic Bond

Figure 28. Structure of Maltose

Lactose
 Galactose + Glucose
 Bond: β-1,4 linkage between C1 of β-D-galactopyranose and
C4 of a-D-glucopyranose
 Broken down by: Lactase
 Also known as milk sugar
Figure 26.B Example of N-Glycosidic Bond
 Is a reducing sugar
Table 2. Disaccharides and linkages

DISACCHARIDES MONOMERS LINKAGE

TWO α-D-
MALTOSE α-1,4-GLYCOSIDIC
GLUCOSE

β- 1,4 -
LACTOSE β-D-GAL & α-D-GLU Figure 29. Structure of Lactose
GLYCOSIDIC
V. POLYSACCHARIDES
α-D-GLU & β-D-
SUCROSE α-1,2-GLYCOSIDIC
FRUC  Condensation products of >10 monosaccharide units
 Linear to branched polymers (does not have definite MW)
β- 1,4 -  Diversity – Monomeric units , Chain length , Type of
CELLOBIOSE TWO β-D-GLUCOSE
GLYCOSIDIC linkage, Degree of branching
 Classification:
TWO α-D-  Hexosans
ISOMALTOSE α-1,6-GLYCOSIDIC  hexose: constituent monosaccharide
GLUCOSE
 Pentosans
 pentose: constituent monosaccharide
 Types:
B. BIOLOGICALLY IMPORTANT DISSACHARIDES  Homoglycans
 Also Homopolymer/Homopolysaccharide
Sucrose  1 type of monosaccharide
 Bond: α1- β2 linkage between C1 of α -D-glucopyranose and  Heteroglycans
C2 of β-D-fructofuranose  Also heteropolymer or heteropolysaccharide
 Broken down by: Sucrase  >1 type of monosaccharide
 Also known as table sugar  Extracellular support for organisms
 Highly soluble in water  Functions:
 Exist only in alpha form  Energy storage – storage forms of monosaccharides
 Non-reducing sugar = because both anomeric carbons C1 of that will be used as fuel (starch and glycogen)
glucose and C2 of fructose are involved in glycosidic bond and  Maintain structural integrity of an organism (cellulose
are not free to react and chitin)

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 IMPORTANT POLYSACCHARIDES

Cellulose
• Chief constituent of plant cell walls (structural)
• Insoluble
• β-D-glucopyranose units linked by β (1-4) bonds (long, straight
chains strengthened by crosslinking hydrogen bonds)
• Mammals lack cellulase (enzyme that hydrolyze β 1-4 bonds),
and thus cannot digest cellulose
• Important source of “bulk” in the diet, and the major component Figure 33. Structure of Glycogen
of dietary fiber
• There is some bacterial metabolism of cellulose in the human VI. TEST FOR SUGARS
colon.
Benedict’s Test
 Identifies reducing sugars (monosaccharide’s and some
disaccharides), which have free ketone or aldehyde functional
groups
 Can be used to test for the presence of glucose in urine
 Benedict’s solution
 Is a weak oxidizing reagent that reacts with simple
Figure 30. Structure of Cellulose carbohydrates when heated and the solution changes its
color
Starch  This reaction is caused by the reducing property of simple
 Is a homopolymer of glucose forming a α-glucosidic chain, carbohydrates
called a glucosan or glucan  Positive Benedict’s Test: Formation of a reddish
 “Vehicles for storage of glucose” precipitate within three minutes. Reducing sugars
 2 main constituents present. Example: Glucose
 Amylose (13%-20%)  Negative Benedict’s Test: No color change (Remains
 Non-branching, linear polymer of glucose Blue). Reducing sugars absent. Example: Sucrose
 Residues linked together by α(1→4) bonds
 Usual conformation: helix with six residues per turn
 Dietary sources: Banana, root vegetables, grains

Figure 31. Structure of Amylose

Figure 34. Reactions in Benedict’s Test
 Amylopectin (80%-87%)
 Branched chains consists of 24 to 30 glucose residues with
Barfoed’s Test
α1 → 4 linkages in the chains and by α1 → 6 linkages at the
branch points  Is a subjective test used to check the presence of
Monosaccharide in an unknown solution.
 Dietary sources: glutinous rice, waxy potato starch, waxy
corn  Barfoed’s Reagent
 a solution of cupric acetate and acetic acid
 Reducing monosaccharides are oxidized by the
copper ion in solution to form a carboxylic acid and
a reddish precipitate of copper (I) oxide within three
minutes. Reducing disaccharides undergo the
same reaction, but do so at a slower rate.
- Positive Test: The formation of reddish
precipitate within 3 minutes
- Negative Test: No formation of a reddish
Figure 32. Structure of Amylopectin precipitate

Glycogen
 Storage polysaccharides in animals, hence called animal starch
 Highly branched structure (more than amylopectin)
 Stored in muscle (β-particles, spherical) and liver (aggregated
β-particles, rosettes)
 12-14 α-D-glucopyranose residues chains with α (1-4) linkage
(in the chain) and α (1-6) linkages (branch)
 More branched than starch
 Less osmotic pressure
 Easily mobilized Figure 35. Reactions in Barfoed’s Test

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Molisch’s Test  Present in beans, whole grains, brown rice, popcorn, nuts,
 Named after a Botanist from Austria, Hans Molisch. cereal (especially bran cereal), oatmeal, vegetables
 Is a delicate synthetic test for the checking of present  Part of the diet that cannot be digested by human
carbohydrates enzymes
 Molisch reagent  Lactose
 a solution of -napthol in 95% ethanol  Major dietary CHO of animal origin
 The test reagent dehydrates pentoses to form furfural  NOTE: most foods derived from animals (ex. meat or
and dehydrates hexoses to form 5-hydroxymethyl fish) contain very little CHO except for small amounts
furfural.The furfurals further react with -naphthol of glycogen and glycolipids
present in the test reagent to produce a purple  Disaccharide found exclusively in milk and milk products
product (reaction not shown).  Primary sites of dietary CHO digestion are the mouth and
- Positive Test: Formation of a purple product at intestinal lumen
the interface of the two layers.  Digestion is catalyzed by glycoside hydrolases
- Negative Test: No formation of a purple (glycosidases) that hydrolyze the glycosidic bonds
product at the interface of the two layers  Final products of CHO digestion are monosaccharides (because
the body can only absorb CHOs in its simplest form)
 Glucose, galactose, and fructose which are absorbed by
cells of the small intestine

Figure 36. Reactions in Molisch’s Test

VIII. CARBOHYDRATE DIGESTION

 In the average US diet, CHO are the largest source of calories

(40%-45% of caloric intake)
 NOTE: although all cells require glucose for metabolic
function, glucose and other sugars are not specifically
required in the diet (Marks’)
 Glucose can be synthesized from dietary protein, and
other sugars (fructose, galactose, etc.) can be
synthesized from glucose Figure 37. CHO Digestion
 Sources of dietary CHO
 Plant starches amylopectin and amylose
 Present in grains (and their products like bread, pasta,
etc.), tubers, and vegetables
 Constitute 50%-60% of CHO calories consumed
 Plant starches are polysaccharides
 Amylose
o The glycosyl residues form a straight chain and are
linked via α-1, 4-glycosidic bonds
o Less digestible (compared to amylopectin) due to
packed structure
 Amylopectin
o A branched chain glucose polymer where its α-1,4-
chains contain branches connected via α-1,6-
glycosidic bonds
o Has the same structure as glycogen, which is found
in animals
 Sucrose
 Major sugar found in fruits and vegetables
 A disaccharide of glucose and fructose
 Sucrose (and small amounts of glucose and fructose)
are the major natural sweeteners found in fruit, honey,
and vegetables
 Also appears in the diet as additives to processed
foods (ex. sweeteners including sucrose and high-
fructose corn syrup)

Sucrose is composed of plant polysaccharides and lignan

(polyphenols found in plants). Lignans are one of the major
classes of phytoestrogens (estrogen-like chemicals) that act as
antioxidants, and is most abundant in flaxseeds.
Figure 38. Summary of CHO digestion in body

 Dietary fiber
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 A. SALIVARY AND PANCREATIC α-AMYLASE Glucoamylase Complex
 Found in the ileum (lower part of small intestine that empties
 Amylase is found in saliva and breaks starch into maltose and into colon/large intestine)
dextrin. This form of amylase is also called "ptyalin"  Catalytic sites
 breaks large, insoluble starch molecules into soluble starches  α-Glucosidase (Maltase-Glucoamylase)
(amylodextrin, erythrodextrin, and achrodextrin)  β-Glucosidase
 Digestion of CHO starts in the mouth  Activities
 Mastication or chewing (mechanical digestion) mixes food  Glucoamylase is an exoglucosidase that splits α-1,4-bonds
with saliva, which contains (salivary) α-Amylase from the non-reducing end of the polysaccharide or limit
 α-Amylase is an endoglucosidase dextrin
 “Attacks” (hydrolyzes) internal α-1, 4-bonds between  Bond farthest from the reducing end is first to be split
glycosyl residues in polysaccharide chains at random  Substrates
intervals  Amylose, amylopectin, glycogen, maltose
 α-Amylase breaks down polysaccharides into smaller
pieces called α-dextrins, which are also polysaccharides Sucrase-Isomaltase Complex
 gastric phase (stomach): no amylase activity
 Found in the jejunum(middle part of small intestine that empties
 pancreatic phase (duodenum): resume of amylase activity
into ileum)
 Hydrolyze 80% of maltase activity
There is no CHO digestion in the stomach! Peristalsis (wave-  Catalytic sites
like muscle contractions) moves food to different parts in the  Sucrose-maltase
digestive tract. Once the bolus (food) enters the stomach, it is  Splits sucrose, maltose, maltotriose
mechanically and chemically digested through churning and  100% of intestine’s ability to hydrolyze sucrose
mixing with both acids (such as hydrochloric acid secreted by  Isomaltase-maltase
parietal cells) and enzymes. The acidic environment in the  Splits α-1,6-bond in limit dextrins and α-1,4-bonds in
stomach inhibits the actions of salivary α-amylase. maltose and maltotriose

 CHO digestion is continued when gastric juice from the stomach Trehalase Complex
enters the duodenum (upper part of small intestine)  Trehalase is only half as long as the other disaccharidases and
 Secretions from the pancreas, containing bicarbonate has only 1 catalytic site
(HCO3) and digestive enzymes (including pancreatic α-  Trehalase
amylase) also enter the duodenum  Hydrolyzes trehalose (a disaccharide made up of 2
 HCO3 neutralizes acidity of stomach contents, thus glycosil units linked by an α-bond between their anomeric
 Pancreatic α-amylase continues to hydrolyze the carbons linked by α-1,1-bond)
starches and glycogen into maltose (disaccharide),  Found in insects and muschrooms
maltotriose, and oligosaccharides
 Also attacks internal α-1, 4-bonds Β-Glycosidase Complex
(Lactase-Glucosylceramidase)
These oligosaccharides are limit dextrins that usually contain  Also found in the jejunum
4-9 glucosyl units with α-1, 6-branches. The 2 glucosyl  Catalytic sites
residues containing this bond eventually become isomaltose  Lactase
(disaccharide). NOTE that α-amylase does not cleave these  Hydrolyzes the β-bond between glucose and galactose in
branched oligosaccharides all the way down to isomaltose. lactase
 Glucosyl Ceramidase (phlorizin hydrolase)
B. DISACCHARIDASES  Hydrolyzes the β-bond between glucose or galactose and
ceramide in glycolipids
OF INTESTINAL BRUSH BORDER MEMBRANE

 Glycosidases, attached to the membrane in the brush border of

C. ABSORPTION OF SUGARS
absorptive cells, break down disaccharides (e.g., lactose,
sucrose, and products of starch digestion) coming from the  The bulk of the dietary sugars (monosaccharides) is absorbed
duodenum in the duodenum and jejunum
 The 4 glycosidases are collectively called small intestinal  Galactose and glucose is absorbed via an active, energy-
disaccharidases requiring process that involves the uptake of sodium ions
 NOTE: glucoamylase is actually an oligosaccharidase  The transport protein is the sodium-dependent glucose co-
transporter 1 (SGLT-1)
 Fructose uptake requires sodium-Independent
monosaccharide transporter (GLUT 5)
 All three of these monosaccharides are transported from the
intestinal mucosal cell in to the portal circulation (towards the
liver) via GLUT 2
 Absorption by the intestinal epithelium
 Glucose is transported to the absorptive cells of the intestine
via facilitated diffusion by sodium-dependent facilitated
transport

D. DIETARY FIBER

(see Appendix 1)
Figure 39. Summary of brush border complexes
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 VIII. GLUCOSE TRANSPORT PROTEINS
Galactose and Fructose are transported through the same
mechanisms as glucose (Na-dependent transporters and
facilitative glucose transporters)

Fructose is absorbed more rapidly when ingested as

sucrose than when it is ingested as a monosaccharide

IX. GLUCOSE TRANSPORT

THROUGH THE BLOOD-BRAIN BARRIER

 GLUT 1 and 3

Figure 40. Glucose Transport Proteins

A. SODIUM-DEPENDENT TRANSPORTERS

 Located at the luminal side of absorptive cells

 Na induces a conformational change in on SGLT-1
 Change allows glucose and galactose to bind
Figure 41. Glucose transport through the capillary endothelium in neural
 As the Na concentration inside the cell increases, Na-K- and non-neural tissues
ATPase on the serosal side of the absorptive cell uses energy
from ATP to pump Na out of the cell and into the blood Table 4. Differences in glucose transport in neural and non-neural
 Transport of glucose and galactose (from low concentration in endothelium
lumen to high concentration inside the cell) Neural Non-Neural
 Promoted by co-transport of Na from a high concentration in Tight junctions between No tight junctions
the lumen to a low concentration inside the cell endothelial cells
Narrow intercellular space Sometimes wide intercellular
B. FACILITATIVE GLUCOSE TRANSPORTERS gaps
Lack of pinocytosis Pinocytosis
 Located on the serosal side of cells Continuous basement Discontinuous basement
 Do not bind to Na membrane membrane
 Movement of glucose is from a high concentration inside the Glucose transporters in both Glucose can diffuse between
cell to lower concentration in the blood membranes cells ad into interstitial fluid
 No expenditure of energy needed
 There are 5 isoforms of glucose transport proteins (see table) X. CLINICAL CORRELATIONS
 Common structural theme is that all isoforms have 12-
membrane spanning domains A. LACTOSE INTOLERANCE
 Note that there are a total of 12 glucose proteins that have
been identified, however only the functions and properties of  A condition in which people have symptoms due to the
GLUT1-5 have been fully described decreased ability to digest lactose, a sugar found in milk
products
Table 3. Glucose Transporters
 Lactase is present predominantly along the brush border
Transporter Tissue Distribution Comments membrane of the differentiated enterocytes lining the villi of the
 Human erythrocyte small intestine.
 Expressed in cell
 Blood-brain barrier  Causes
types with barrier
 Blood-retinal barrier  Due to lack of enzyme lactase
GLUT1 fxtns; high affinity
 Blood-placental barrier glucose transport  Primary: when the amount of lactase declines as people
 Blood-testis barrier system age
 Secondary: lactose intolerance is due to injury to the
 Liver small intestine (may be from infection, kwashiorkor,
 High capacity, low
 Kidney colitis, inflammatory bowel disease, etc.)
affinity transporter  Diagnosis
GLUT2  Pancreatic B-cell
 Used as glucose  May be confirmed if symptoms resolve following eliminating
 Serosal surface of sensor in pancreas
intestinal mucosa cells lactose from the diet
 Major transporter
GLUT3  Brain (neurons) in CNS; high B. FRUCTOSE INTOLERANCE
affinity system
 Adipose tissue  Insulin-sensitive  Inability to absorb fructose efficiently
GLUT4  Skeletal muscle transporter; high  Causes
 Heart muscle affinity system  Abnormalities in the fructose transporter
 Intestinal epithelium  Not due to an enzyme, since fructose is already a
 Fructose
GLUT5 monosaccharide
 Spermatozoa transporter
 Presence of bacteria that may inhibit the transporter
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 C. HEREDITARY FRUCTOSE INTOLERANCE G. HYPERGLYCEMIA

 Autosomal recessive disorder of fructose metabolism  High blood glucose levels because glucose cannot enter the
 Causes cells
 Fructose aldolase B deficiency due to lack in any of the  Bloos sugar:
following enzymes  above 7 mmol/L fasting or before a meal
 Aldolase A in peripheral tissue  above 10 mmol/L two hours after a meal
 Fructokinase in peripheral tissue  Causes:
 Aldolase B in the liver  a diet abnormally high in carbohydrates
 Leads to colonic bacteria metabolism of fructose and the  reduced physical activity
generation of organic acids and gases  insufficient insulin and/or antidiabetic medication (dosage
error or a skipped dose)
D. SUCROSE INTOLERANCE  Physical stress or Psychological stress
 taking certain drugs (e.g.: cortisone)
 A rare genetic deficiency of sucrose
 Also known as sucrase-isomaltase deficiency H. MANNOSIDOSIS
 Sucrose and isomaltase can be found as a heterodimer
(sucrose-maltase)  A rare and hereditary lysosome storage disorder
 Attributed to isomaltose and starch intolerance
 Leads to diarrhea and flatulence Alpha-mannosidosis
 A defective alpha-mannosidase enzyme (helps breakdown
E. GALACTOSEMIA complex sugars derived from glycoproteins in the lysosome
 Causes sugar build up and impairs cell function.
 Result of failure in metabolizing galactose  Leads to death during early childhood due to deterioration of
 Leads to cataracts the central nervous system.
 Symptoms: reduced hearing, mental disabilities, susceptibility to
Classic galatosemia bacterial infections, and skeletal deformities. The course of the
 also known as type I, is the most common and most severe disease is progressive.
form of the condition
 causes: Beta-mannosidosis
 lack of energy (lethargy),  Disorder of oligosaccharide metabolism caused by decreased
 failure to gain weight and grow as expected activity of the enzyme beta-mannosidase.
 yellowing of the skin and whites of the eyes (jaundice)  Respiratory infections, angiokeratoma, hearing loss and
 liver damage, and abnormal bleeding. intellectual disability. intellectual disability.
Females with classic galactosemia may develop reproductive  Because of its rarity, and non-specific clinical findings, beta-
problems caused by an early loss of function of the ovaries mannosidosis can go undiagnosed until adulthood, where it can
(premature ovarian insufficiency). present with intellectual disability and behavioral problems,
including aggression.
Type II and III
 Galactosemia type II or galactokinase deficiency I. GLUCOSE-GALACTOSE MALABSORPTION (GGM)
 Autosomal recessive
 Accumulation of galactose or galactitol  Mutation in the gene can encodes sodium/glucose cotransporter
 Cataracts I the first week or months of life  The SLC5A1 gene provides instructions for producing a
 Galactosemia type III or galactose epimerase deficiency sodium/glucose cotransporter protein called SGLT1.
 Liver failure  Cells that line the intestine cannot absorb and take in two
specific sugars, namely glucose and galactose
 Renal failure
 Difficulty in properly digestion → accumulation of sugars in the
 Splenomegaly
gut → water remains outside of the body’s cells → diarrhea and
 Cataracts
dehydration
 Sensorineural hearing loss
REFERENCES
F. HYPOGLYCEMIA Lecturer’s PPT
Mark’s Basic Biochemistry in Medicine, 4th Ed.
 Low blood glucose levels Harper’s Biochemistry, 28th Ed.
 Caused by deficiencies in certain enzymes of CHO metabolism 2020C Trans
 Reactive hypoglycemia
 Occurs within a few hours after a meal.
 Overproduction of insulin.
 Risk for developing diabetes.
 Non-reactive hypoglycemia
 not necessarily related to meals and may be due to an
underlying disease.
 Causes of non-reactive, or fasting, hypoglycemia:
 some medications,
 excess amounts of alcohol (stops liver from producing
glucose)
 any disorder that affects the liver, heart, or kidneys
 some eating disorders, such as anorexia
 pregnancy
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 Appendix 1. Dietary Fiber, adapted from Marks’ Basic Medical Biochemistry, p.503

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